Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore

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

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan

We report the structural changes induced by Brønsted acidic site deprotonation in a zeolite with MFI structure as a function of temperature up to 430°C using in situ Al K-edge X-ray absorption fine structure spectroscopy (XAFS). At ambient conditions, the protons are present as hydrated hydronium ions (H3O+(H2O)n) that are ion-paired to the anionic, Al tetrahedral (T) site. At elevated temperatures, loss of water molecules hydrating the hydronium ions leads to an unstable free hydronium ion that disso-ciates to form the hydroxylated T-site. The formation of this (-O3)-Al-(OH-) species leads to the elongation of one of the four Al-O bondsmore » and causes significant distortion of the tetrahedral symmetry about the Al atom. This distortion leads to the appearance of new pre-edge features in the Al K-edge X-ray absorption near edge structure (XANES) spectra. The pre-edge peak assignment is confirmed by time-dependent density functional theory calculation of the XANES spectrum. The XANES spectra are also sensitive to solutes or solvent that are in proximity to the T-site. A second structural transition occurs at about the same temperature, namely the conversion of a minor fraction of extra-framework octahedral Al present in the sample at ambient conditions to a tetrahedral species through the de-coordination of H2O-ligands. Both IR spectroscopy and thermogravimetric analysis (TGA) are further used to confirm the overall chemical transformation of the T-site.« less

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

PubMed Central

Getty, Kendra; Delgado-Jaime, Mario Ulises

2010-01-01

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

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

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.

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.

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.

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.

The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

2016-05-01

Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

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.

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+/ΣTi in meteoritic hibonite when the synthetic hibonite standards are crystal-chemically matched to the natural samples and are measured during the same analytical session as the meteoritic hibonites.

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.

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

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.

Local atomic and electronic structures in ferromagnetic topological insulator Cr-doped (BixSb1-x) 2Te3 studied by XAFS and ab initio calculations

NASA Astrophysics Data System (ADS)

Liu, Zhen; Wei, Xinyuan; Wang, Jiajia; Pan, Hong; Ji, Fuhao; Ye, Mao; Yang, Zhongqin; Qiao, Shan

2015-09-01

The local atomic and electronic structures around the dopants in Cr-doped (BixSb1 -x )2Te3 are studied by x-ray absorption fine structure (XAFS) measurements and first-principles calculations. Both Cr and Bi are confirmed substituting Sb sites (CrSb and BiSb). The six nearest Te atoms around Cr move towards Cr and shorten the Cr-Te bond lengths to 2.76 Å and 2.77 Å for x =0.1 and x =0.2 , respectively. Importantly, we reveal the hybridization between the Sb/Te p states and Cr d states by the presence of a pre-edge peak at Cr K -absorption edge, which is also supported by our ab initio calculations. These findings provide important clues to understand the mechanism of ferromagnetic order in this system with quantum anomalous Hall effect.

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.

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.

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

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

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

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas

Here, the connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b 1) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterizedmore » by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b 1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b 1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b 1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.« less

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

DOE PAGES

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas; ...

2018-04-14

Here, the connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b 1) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterizedmore » by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b 1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b 1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b 1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.« less

Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions† †Electronic supplementary information (ESI) available: Experimental methods; UV-vis absorption spectrum and crystallographic data for 3; fits to Cu K pre-edge XANES spectra; details of DFT, CASSCF, and MR-DDCI3 computational experiments; optimized atomic coordinates for all complexes. CCDC 1031118 and 1031119. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03294b Click here for additional data file. Click here for additional data file.

PubMed Central

Williams, Kamille D.; Dai, Xuliang; Sproules, Stephen; DeBeer, Serena

2015-01-01

Three [Me2NN]Cu(η2-L2) complexes (Me2NN = HC[C(Me)NAr]2; L2 = PhNO (2), (3), PhCH 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CH2 (4); Ar = 2,6-Me2-C6H3; ArF = 3,5-(CF3)2-C6H3) have been studied by Cu K-edge X-ray absorption spectroscopy, as well as single- and multi-reference computational methods (DFT, TD-DFT, CASSCF, MRCI, and OVB). The study was extended to a range of both known and theoretical compounds bearing 2p-element donors as a means of deriving a consistent view of how the pre-edge transition energy responds in systems with significant ground state covalency. The ground state electronic structures of many of the compounds under investigation were found to be strongly influenced by correlation effects, resulting in ground state descriptions with majority contributions from a configuration comprised of a Cu(ii) metal center anti-ferromagentically coupled to radical anion O2, PhNO, and ligands. In contrast, the styrene complex 4, which displays a Cu K pre-edge transition despite its formal d10 electron configuration, exhibits what can best be described as a Cu(i):(styrene)0 ground state with strong π-backbonding. The Cu K pre-edge features for these complexes increase in energy from 1 to 4, a trend that was tracked to the percent Cu(ii)-character in the ground state. The unexpected shift to higher pre-edge transition energies with decreasing charge on copper (Q Cu) contributed to an assignment of the pre-edge features for these species as arising from metal-to-ligand charge transfer instead of the traditional Cu1s → Cu3d designation. PMID:29308158

Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes

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

Spanjers, Charles S.; Guillo, Pascal; Tilley, T. Don

X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti–O–(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique featuresmore » for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O–X (X = C, Si, or Ge) antibonding orbitals.« less

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.

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

Determination of oxidation state of iron in normal and pathologically altered human aortic valves

NASA Astrophysics Data System (ADS)

Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

2015-12-01

In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe3+ is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe3+ form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

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.

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

PubMed

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

2013-11-18

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

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.

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.

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.

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.

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.

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

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

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.

X-ray absorption in insulators with non-Hermitian real-time time-dependent density functional theory.

PubMed

Fernando, Ranelka G; Balhoff, Mary C; Lopata, Kenneth

2015-02-10

Non-Hermitian real-time time-dependent density functional theory was used to compute the Si L-edge X-ray absorption spectrum of α-quartz using an embedded finite cluster model and atom-centered basis sets. Using tuned range-separated functionals and molecular orbital-based imaginary absorbing potentials, the excited states spanning the pre-edge to ∼20 eV above the ionization edge were obtained in good agreement with experimental data. This approach is generalizable to TDDFT studies of core-level spectroscopy and dynamics in a wide range of materials.

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.

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.

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2014-12-14

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

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.

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.

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

Core-shell photoabsorption and photoelectron spectra of gas-phase pentacene: experiment and theory.

PubMed

Alagia, Michele; Baldacchini, Chiara; Betti, Maria Grazia; Bussolotti, Fabio; Carravetta, Vincenzo; Ekström, Ulf; Mariani, Carlo; Stranges, Stefano

2005-03-22

The C K-edge photoabsorption and 1s core-level photoemission of pentacene (C22H14) free molecules are experimentally measured, and calculated by self-consistent-field and static-exchange approximation ab initio methods. Six nonequivalent C atoms present in the molecule contribute to the C 1s photoemission spectrum. The complex near-edge structures of the carbon K-edge absorption spectrum present two main groups of discrete transitions between 283 and 288 eV photon energy, due to absorption to pi* virtual orbitals, and broader structures at higher energy, involving sigma* virtual orbitals. The sharp absorption structures to the pi* empty orbitals lay well below the thresholds for the C 1s ionizations, caused by strong excitonic and localization effects. We can definitely explain the C K-edge absorption spectrum as due to both final (virtual) and initial (core) orbital effects, mainly involving excitations to the two lowest-unoccupied molecular orbitals of pi* symmetry, from the six chemically shifted C 1s core orbitals.

Core-shell photoabsorption and photoelectron spectra of gas-phase pentacene: Experiment and theory

NASA Astrophysics Data System (ADS)

Alagia, Michele; Baldacchini, Chiara; Betti, Maria Grazia; Bussolotti, Fabio; Carravetta, Vincenzo; Ekström, Ulf; Mariani, Carlo; Stranges, Stefano

2005-03-01

The C K-edge photoabsorption and 1s core-level photoemission of pentacene (C22H14) free molecules are experimentally measured, and calculated by self-consistent-field and static-exchange approximation ab initio methods. Six nonequivalent C atoms present in the molecule contribute to the C 1s photoemission spectrum. The complex near-edge structures of the carbon K-edge absorption spectrum present two main groups of discrete transitions between 283 and 288eV photon energy, due to absorption to π* virtual orbitals, and broader structures at higher energy, involving σ* virtual orbitals. The sharp absorption structures to the π* empty orbitals lay well below the thresholds for the C 1s ionizations, caused by strong excitonic and localization effects. We can definitely explain the C K-edge absorption spectrum as due to both final (virtual) and initial (core) orbital effects, mainly involving excitations to the two lowest-unoccupied molecular orbitals of π* symmetry, from the six chemically shifted C 1s core orbitals.

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 potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

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 potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

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.

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

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.

Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

NASA Technical Reports Server (NTRS)

Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

2004-01-01

We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

Intermolecular Interactions of Pyridine in Liquid Phase and Aqueous Solution Studied by Soft X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Nagasaka, Masanari; Yuzawa, Hayato; Kosugi, Nobuhiro

2018-05-01

Intermolecular interactions of pyridine in liquid and in aqueous solution are studied by using soft X-ray absorption spectroscopy (XAS) at the C, N, and O K-edges. XAS of liquid pyridine shows that the N 1s→π* peak is blue shifted and the C 1s→π* peak of the meta and para sites is red shifted, respectively, as compared with XAS of pyridine gas. These shifts in liquid are smaller than those in clusters, indicating that the intermolecular interaction of liquid pyridine is weaker than that of pyridine cluster, as supported by the combination of quantum chemical calculations of the core excitation and molecular dynamics simulations of the liquid structure. On the other hand, XAS spectra of aqueous pyridine solutions (C5H5N)x(H2O)1-x measured at different molar fractions show that in the pyridine rich region, x>0.7, the C and N 1s→π* peak energies are not so different from pure liquid pyridine (x=1.0). In this region, antiparallel displaced structures of pyridine molecules are dominant as in pure pyridine liquid. In the O K-edge XAS, the pre-edge peaks sensitive to the hydrogen bond (HB) network of water molecules show the red shift of -0.15 eV from that of bulk water, indicating that small water clusters with no large-scale HB network are formed in the gap space of structured pyridine molecules. In the water rich region, 0.7>x, the N 1s→π* peaks and the O 1s pre-edge peaks are blue shifted, and the C 1s→π* peaks of the meta and para sites are red-shifted by increasing molar fraction of water. The HB network of bulk water is dominant, but quantum chemical calculations indicate that small pyridine clusters with the HB interaction between the H atom in water and the N atom in pyridine are still existent even in very dilute pyridine solutions.

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.

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

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.

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

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.

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.

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.

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

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.

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

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...

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.

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

PubMed

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

2015-03-01

Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is transformed into Fe(2+), while the local Fe-O coordination number of 4-5 is maintained, suggesting that the reduction involves a rearrangement of the oxygen neighbours rather than their removal. In conclusion, the variogram-based analysis of Fe K-edge spectra proves to be very useful in catalysis research.

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...

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

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.

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.

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

Observation of high-spin mixed oxidation state of cobalt in ceramic Co3TeO6

NASA Astrophysics Data System (ADS)

Singh, Harishchandra; Ghosh, Haranath; Chandrasekhar Rao, T. V.; Sinha, A. K.; Rajput, Parasmani

2014-12-01

We report coexistence of high spin Co3+ and Co2+ in ceramic Co3TeO6 using X-ray Absorption Near Edge Structure (XANES), DC magnetization, and first principles ab-initio calculations. The main absorption line of cobalt Co K-edge XANES spectra, along with a linear combination fit, led us to estimate relative concentration of Co2+ and Co3+as 60:40. The pre edge feature of XANES spectrum shows crystal field splitting of ˜1.26 eV between eg and t2g states, suggesting a mixture of high spin states of both Co2+ and Co3+. Temperature dependent high field DC magnetization measurements reveal dominant antiferromagnetic order with two Neel temperatures (TN1 ˜ 29 K and TN2 ˜ 18 K), consistent with single crystal study. A larger effective magnetic moment is observed in comparison to that reported for single crystal (which contains only Co2+), supports our inference that Co3+ exists in high spin state. Furthermore, we show that both Co2+ and Co3+ being in high spin states constitute a favorable ground state through first principles ab-initio calculations, where Rietveld refined synchrotron X-ray diffraction data are used as input.

Communication: X-ray excited optical luminescence from TbCl3 at the giant resonance of terbium

NASA Astrophysics Data System (ADS)

Heigl, F.; Jürgensen, A.; Zhou, X.-T.; Hu, Y.-F.; Zuin, L.; Sham, T. K.

2013-02-01

We have studied the optical recombination channels of TbCl3 using x-ray excited optical luminescence at the N4,5 absorption edge of Tb (giant resonance) in both the energy and time domain. The luminescence exhibits a relatively fast 5D3, and a slow 5D4 decay channel in the blue and green, respectively. The rather short lifetime of the 5D3 state indicates that the decay is mainly driven by Tb-Tb ion interaction via non-radiative energy transfer (cross-relaxation). At the giant resonance the X-ray Absorption Near Edge Structure (XANES) recorded using partial photoluminescence yield is inverted. In the pre-edge region the contrast of the spectral feature is significantly better in optical XANES than in total electron yield. Changes in the intensity of 5D3-7F5 (544 nm) and 5D4-7F6 (382 nm) optical transitions as the excitation energy is tuned across the giant resonance are also noted. The results provide detailed insight into the dynamics of the optical recombination channels and an alternative method to obtain high sensitivity, high energy resolution XANES at the giant resonance of light emitting rare-earth materials.

Micro-XANES Determination Fe Speciation in Natural Basalts at Mantle-Relevant fO2

NASA Astrophysics Data System (ADS)

Fischer, R.; Cottrell, E.; Lanzirotti, A.; Kelley, K. A.

2007-12-01

We demonstrate that the oxidation state of iron (Fe3+/ΣFe) can be determined with a precision of ±0.02 (10% relative) on natural basalt glasses at mantle-relevant fO2 using Fe K-edge X-ray absorption near edge structure (XANES) spectroscopy. This is equivalent to ±0.25 log unit resolution relative to the QFM buffer. Precise determination of the oxidation state over this narrow range (Fe3+/ΣFe=0.06-0.30) and at low fO2 (down to QFM-2) relies on appropriate standards, high spectral resolution, and highly reproducible methods for extracting the pre-edge centroid position. We equilibrated natural tholeiite powder in a CO/CO2 gas mixing furnace at 1350°C from QFM-3 to QFM+2 to create six glasses of known Fe3+/ΣFe, independently determined by Mössbauer spectroscopy. XANES spectra were collected at station X26A at NSLS, Brookhaven Natl. Lab, in fluorescence mode (9 element Ge array detector) using both Si(111) and Si(311) monochromators. Generally, the energy position of the 1s→3d (pre-edge) transition centroid is the most sensitive monitor of Fe oxidation state using XANES. For the mixture of Fe oxidation states in these glasses and the resulting coordination geometries, the pre-edge spectra are best defined by two multiple 3d crystal field transitions. The Si(311) monochromator, with higher energy resolution, substantially improved spectral resolution for the 1s→3d transition. Dwell times of 5s at 0.1eV intervals across the pre-edge region yielded spectra with the 1s→3d transition peaks clearly resolved. The pre-edge centroid position is highly sensitive to the background subtraction and peak fitting procedures. Differences in fitting models result in small but significant differences in the calculated peak area of each pre-edge multiplet, and the relative contribution of each peak to the calculated centroid. We assessed several schemes and obtained robust centroid positions by simultaneously fitting the background with a damped harmonic oscillator (DHO) function and pre-edge features with two Gaussians over a sub-sample of the pre-edge region (7110-7120 eV). We found that the relation between Fe3+/ΣFe and the centroid energy is non-linear over this fO2 range, which is expected if the coordination environment changes with oxidation state. ΔQFM is linearly related (R2=0.99) to the centroid position. This new calibration allows the oxidation states of natural mantle melts to be discriminated with high spatial resolution (9μm). We apply the new calibration to determination of Fe3+/ΣFe in natural basaltic glasses and olivine-hosted glass inclusions (Cottrell et al. & Kelley et al., this meeting).

XANES analysis of dried and calcined bones.

PubMed

Rajendran, Jayapradhi; Gialanella, Stefano; Aswath, Pranesh B

2013-10-01

The structure of dried and calcined bones from chicken, bovine, deer, pig, sheep and chamois was examined using X-ray Absorption Near Edge Structure (XANES) spectroscopy. The oxygen K-edge absorption edge indicates that the surface of dried bone has a larger proportion of carbonate than the interior that is made up of phosphates. The phosphorus L and K edge clearly indicate that pyrophosphates, α-tricalcium phosphate (α-TCP) and hydrogen phosphates of Ca do not exist in either the dried bone or calcined bone and phosphorus exists as either β-tricalcium phosphate (β-TCP) or hydroxyapatite, both in the dried and calcined conditions. The Ca K-edge analysis indicates that β-TCP is the likely form of phosphate in both the dried and calcined conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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

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

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.

Ultrafast X-Ray Absorption Spectroscopy of Isochorically Heated Warm Dense Matter

NASA Astrophysics Data System (ADS)

Engelhorn, Kyle Craig

This dissertation will present a series of new tools, together with new techniques, focused on the understanding of warm and dense matter. We report on the development of a high time resolution and high detection efficiency x-ray camera. The camera is integrated with a short pulse laser and an x-ray beamline at the Advanced Light Source synchrotron. This provides an instrument for single shot, broadband x-ray absorption spectroscopy of warm and dense matter with 2 picosecond time resolution. Warm and dense matter is created by isochorically heating samples of known density with an ultrafast optical laser pulse, and X-ray absorption spectroscopy probes the unoccupied electronic density of states before the onset of hydrodynamic expansion and electron-ion equilibrium is reached. Measured spectra from a variety of materials are compared with first principle molecular dynamics and density functional theory calculations. In heated silicon dioxide spectra, two novel pre-edge features are observed, a peak below the band gap and absorption within the band gap, while a reduction was observed in the features above the edge. From consideration of the calculated spectra, the peak below the gap is attributed to valence electrons that have been promoted to the conduction band, the absorption within the gap is attributed to broken Si-O bonds, and the reduction above the edge is attributed to an elevated ionic temperature. In heated copper spectra, a time-dependent shift and broadening of the absorption edge are observed, consistent with and elevated electron temperature. The temporal evolution of the electronic temperature is accurately determined by fitting the measured spectra with calculated spectra. The electron-ion equilibration is studied with a two-temperature model. In heated nickel spectra, a shift of the absorption edge is observed. This shift is found to be inconsistent with calculated spectra and independent of incident laser fluence. A shift of the chemical potential is applied to the calculated spectra to obtain satisfactory agreement with measured spectra.

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.

Structuring β-Ga2O3 photonic crystal photocatalyst for efficient degradation of organic pollutants.

PubMed

Li, Xiaofang; Zhen, Xiuzheng; Meng, Sugang; Xian, Jiangjun; Shao, Yu; Fu, Xianzhi; Li, Danzhen

2013-09-03

Coupling photocatalysts with photonic crystals structure is based on the unique property of photonic crystals in confining, controlling, and manipulating the incident photons. This combination enhances the light absorption in photocatalysts and thus greatly improves their photocatalytic performance. In this study, Ga2O3 photonic crystals with well-arranged skeleton structures were prepared via a dip-coating infiltration method. The positions of the electronic band absorption for Ga2O3 photonic crystals could be made to locate on the red edge, on the blue edge, and away from the edge of their photonic band gaps by changing the pore sizes of the samples, respectively. Particularly, the electronic band absorption of the Ga2O3 photonic crystal with a pore size of 135 nm was enhanced more than other samples by making it locate on the red edge of its photonic band gap, which was confirmed by the higher instantaneous photocurrent and photocatalytic activity for the degradation of various organic pollutants under ultraviolet light irradiation. Furthermore, the degradation mechanism over Ga2O3 photonic crystals was discussed. The design of Ga2O3 photonic crystals presents a prospective application of photonic crystals in photocatalysis to address light harvesting and quantum efficiency problems through manipulating photons or constructing photonic crystal structure as groundwork.

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.

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.

Reverse engineering the ancient ceramic technology based on X-ray fluorescence spectromicroscopy

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

Sciau, Philippe; Leon, Yoanna; Goudeau, Philippe

2011-07-06

We present results of X-ray fluorescence (XRF) microprobe analyses of ancient ceramic cross-sections aiming at deciphering the different firing protocols used for their production. Micro-focused XRF elemental mapping, Fe chemical mapping and Fe K-edge X-ray absorption near edge structure spectroscopy were performed on pre-sigillata ceramics from southern Gaul, and terra Sigillata vessels from Italy and southern Gaul. Pieces from the different workshops and regions showed significant difference in the starting clay material, clay conditioning and kiln firing condition. By contrast, sherds from the same workshop exhibited more subtle differences and possible misfirings. Understanding the precise firing conditions and protocols wouldmore » allow recreation of kilns for various productions. Furthermore, evolution and modification of kiln design would shed some light on how ancient potters devised solutions to diverse technological problems they encountered.« less

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.

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

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

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

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE PAGES

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

2017-06-22

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

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.

XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

NASA Astrophysics Data System (ADS)

Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2016-08-01

X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

USGS Publications Warehouse

Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

2011-01-01

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and M??ssbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, r??merite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3??5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750-4000cm-1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. M??ssbauer spectra of selected samples were obtained at room temperature and 80K for ferric minerals jarosite and rhomboclase and mixed ferric-ferrous minerals r??merite, voltaite, and copiapite. Values of Fe2+/[Fe2++Fe3+] determined by M??ssbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases. ?? 2011 Elsevier B.V.

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 deconvolution algorithm is proposed to minimize truncation effects in Fourier filtering.

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

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

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.

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.

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

Progress in thin-film silicon solar cells based on photonic-crystal structures

NASA Astrophysics Data System (ADS)

Ishizaki, Kenji; De Zoysa, Menaka; Tanaka, Yoshinori; Jeon, Seung-Woo; Noda, Susumu

2018-06-01

We review the recent progress in thin-film silicon solar cells with photonic crystals, where absorption enhancement is achieved by using large-area resonant effects in photonic crystals. First, a definitive guideline for enhancing light absorption in a wide wavelength range (600–1100 nm) is introduced, showing that the formation of multiple band edges utilizing higher-order modes confined in the thickness direction and the introduction of photonic superlattice structures enable significant absorption enhancement, exceeding that observed for conventional random scatterers. Subsequently, experimental evidence of this enhancement is demonstrated for a variety of thin-film Si solar cells: ∼500-nm-thick ultrathin microcrystalline silicon cells, few-µm-thick microcrystalline silicon cells, and ∼20-µm-thick thin single-crystalline silicon cells. The high short-circuit current densities and/or efficiencies observed for each cell structure confirm the effectiveness of using multiple band-edge resonant modes of photonic crystals for enhancing broadband absorption in actual solar cells.

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.

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 its valence electronic structure from that of the formally trivalent compounds (BDI)AlX2 and (BDI)AlR2. The work shows that Al K-edge XANES spectroscopy can be used to provide valuable insight into electronic structure and reactivity relationships for main-group coordination compounds.

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

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.

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.

Synchrotron applications in wood preservation and deterioration

Treesearch

Barbara L. Illman

2003-01-01

Several non-intrusive synchrotron techniques are being used to detect and study wood decay. The techniques use high intensity synchrotron-generated X-rays to determine the atomic structure of materials with imaging, diffraction, and absorption. Some of the techniques are X-ray absorption near edge structure (XANES), X-ray fluorescence spectroscopy (XFS), X-ray...

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study of cobalt effect on structural and optical properties of Dy doped ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Pawan; Pandey, Praveen C.

2018-05-01

The present study has been carried out to investigate the effect of Co doping on structural and optical properties of Dy doped ZnO nanoparticles. We have prepared pure Zinc oxide, Dy (1%) doped ZnO and Dy (1%) doped ZnO co-doped with Co(2%) with the help of simple sol-gel combustion method. The structural analysis carried out using X-ray diffraction spectra (XRD) indicates substitution of Dy and Co at Zn site of ZnO crystal structure and hexagonal crystal structure without any secondary phase formation in all the samples. The surface morphology was analyzed by transmission electron microscopy (TEM). Absorption study indicates that Dy doping causes a small shift in band edge, while Co co-doping results significant change is absorption edge as well as introduce defect level absorption in the visible region. The band gap of samples decreases due to Dy and Co doping, which can be attributed to defect level formation below the conduction band in the system.

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.

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.

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.

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

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

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

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.

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

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.

Second-harmonic generation at angular incidence in a negative-positive index photonic band-gap structure.

PubMed

D'Aguanno, Giuseppe; Mattiucci, Nadia; Scalora, Michael; Bloemer, Mark J

2006-08-01

In the spectral region where the refractive index of the negative index material is approximately zero, at oblique incidence, the linear transmission of a finite structure composed of alternating layers of negative and positive index materials manifests the formation of a new type of band gap with exceptionally narrow band-edge resonances. In particular, for TM-polarized (transverse magnetic) incident waves, field values that can be achieved at the band edge may be much higher compared to field values achievable in standard photonic band-gap structures. We exploit the unique properties of these band-edge resonances for applications to nonlinear frequency conversion, second-harmonic generation, in particular. The simultaneous availability of high field localization and phase matching conditions may be exploited to achieve second-harmonic conversion efficiencies far better than those achievable in conventional photonic band-gap structures. Moreover, we study the role played by absorption within the negative index material, and find that the process remains efficient even for relatively high values of the absorption coefficient.

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

Water and the oxidation state of subduction zone magmas.

PubMed

Kelley, Katherine A; Cottrell, Elizabeth

2009-07-31

Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe3+/SigmaFe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H2O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe3+/SigmaFe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H2O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

The redox state of iron in the matrix of CI, CM and metamorphosed CM chondrites by XANES spectroscopy

NASA Astrophysics Data System (ADS)

Beck, P.; De Andrade, V.; Orthous-Daunay, F.-R.; Veronesi, G.; Cotte, M.; Quirico, E.; Schmitt, B.

2012-12-01

Carbonaceous chondrites record the action of water at some point of their petrological history. These meteorites are usually connected to low albedo asteroid, which present visible/near-IR absorption explained by iron related absorption within phyllosilicates and oxides. In order to obtain quantitative insight into the mineralogy of iron-bearing phases, we have measured X-ray absorption near-edge spectroscopy at the iron K-edge of matrix from carbonaceous chondrites. This method enables to constrain the redox state and environment of iron in these meteorites. For this study, we selected seven CM chondrites and the CI Orgueil, expected to span a range of aqueous alteration degrees. Our analysis of the pre-edge features show that the redox state of Orgueil (CI) is dominated by octahedral Fe and that the Fe3+/(Fe3++Fe2+) atomic ratio is above 80%. Full-inversion of the spectra suggests that the iron budget is dominated by iron oxides, with additional contributions from phyllosilicate. In the case of the CM, the iron speciation appears different that in the case of Orgueil. Cronstedtite is identified from the inversion of the spectra, and suggested by the presence of significant amount of tetrahedral Fe3+. Within the CM chondrites, a trend of aqueous alteration appears presents, and which is roughly correlated to the scheme defined by Rubin et al. (2007). This trend is characterized by an increase in the amount of iron oxides. Two shock metamorphosed CM are present in our dataset (PCA 91008, WIS 91600). If WIS 91600 does not appear distinguishable, from the CM trend, in the case of PCA 91008, shock metamorphism did impact the pre-edge intensity and an increased amount of anhydrous silicates is found. Although the matrix was dehydrated, significant amount of Fe3+ is still present, providing a memory of the aqueous alteration.

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

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Homma-Takeda, Shino

2017-01-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate. PMID:28244440

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Shimada, Yoshiya; Homma-Takeda, Shino

2017-03-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III -edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.

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.

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.

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.

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.

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.

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.

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.

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.

Optical properties of graphene nanoflakes: Shape matters.

PubMed

Mansilla Wettstein, Candela; Bonafé, Franco P; Oviedo, M Belén; Sánchez, Cristián G

2016-06-14

In recent years there has been significant debate on whether the edge type of graphene nanoflakes (GNFs) or graphene quantum dots (GQDs) are relevant for their electronic structure, thermal stability, and optical properties. Using computer simulations, we have proven that there is a fundamental difference in the absorption spectra between samples of the same shape, similar size but different edge type, namely, armchair or zigzag edges. These can be explained by the presence of electronic structures near the Fermi level which are localized on the edges. These features are also evident from the dependence of band gap on the GNF size, which shows three very distinct trends for different shapes and edge geometries.

Optical properties of graphene nanoflakes: Shape matters

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

Mansilla Wettstein, Candela; Bonafé, Franco P.; Sánchez, Cristián G., E-mail: cgsanchez@fcq.unc.edu.ar

In recent years there has been significant debate on whether the edge type of graphene nanoflakes (GNFs) or graphene quantum dots (GQDs) are relevant for their electronic structure, thermal stability, and optical properties. Using computer simulations, we have proven that there is a fundamental difference in the absorption spectra between samples of the same shape, similar size but different edge type, namely, armchair or zigzag edges. These can be explained by the presence of electronic structures near the Fermi level which are localized on the edges. These features are also evident from the dependence of band gap on the GNFmore » size, which shows three very distinct trends for different shapes and edge geometries.« less

XAS study of TiO2-based nanomaterials

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Local structural variation with oxygen fugacity in Fe 2SiO 4+x fayalitic iron silicate melts

DOE PAGES

Alderman, O.L.G.; Lazareva, L.; Wilding, M. C.; ...

2017-01-07

Here, the structure of molten Fe 2SiO 4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe 3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature ( T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and –5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K andmore » –2.1(3) < ΔFMQ < +4.4(3) log units. Fe 3+ contents, x = Fe 3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, n FeO, close to 5 for all Fe 3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < n FeO < 4.7(1). There is limited evidence for a linear trend n FeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean r FeO lie close to 2.06 Å, consistent with n FeO close to 5. These observations suggest that Fe 2+ is less efficient at stabilizing tetrahedral Fe 3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe 3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.« less

Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Lazareva, L.; Wilding, M. C.; Benmore, C. J.; Heald, S. M.; Johnson, C. E.; Johnson, J. A.; Hah, H.-Y.; Sendelbach, S.; Tamalonis, A.; Skinner, L. B.; Parise, J. B.; Weber, J. K. R.

2017-04-01

The structure of molten Fe2SiO4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature (T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and -5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K and -2.1(3) < ΔFMQ < +4.4(3) log units. Fe3+ contents, x = Fe3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe-O coordination numbers, nFeO, close to 5 for all Fe3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < nFeO < 4.7(1). There is limited evidence for a linear trend nFeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe-O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean rFeO lie close to 2.06 Å, consistent with nFeO close to 5. These observations suggest that Fe2+ is less efficient at stabilizing tetrahedral Fe3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.

Determination of Scattering and Absorption Coefficients for Plasma-Sprayed Yttria-Stabilized Zirconia Thermal Barrier Coatings at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Eldridge, Jeffrey I.; Spuckler, Charles M.; Markham, James R.

2009-01-01

The temperature dependence of the scattering and absorption coefficients for a set of freestanding plasma-sprayed 8 wt% yttria-stabilized zirconia (8YSZ) thermal barrier coatings (TBCs) was determined at temperatures up to 1360 C in a wavelength range from 1.2 micrometers up to the 8YSZ absorption edge. The scattering and absorption coefficients were determined by fitting the directional-hemispherical reflectance and transmittance values calculated by a four-flux Kubelka Munk method to the experimentally measured hemispherical-directional reflectance and transmittance values obtained for five 8YSZ thicknesses. The scattering coefficient exhibited a continuous decrease with increasing wavelength and showed no significant temperature dependence. The scattering is primarily attributed to the relatively temperature-insensitive refractive index mismatch between the 8YSZ and its internal voids. The absorption coefficient was very low (less than 1 per centimeter) at wavelengths between 2 micrometers and the absorption edge and showed a definite temperature dependence that consisted of a shift of the absorption edge to shorter wavelengths and an increase in the weak absorption below the absorption edge with increasing temperature. The shift in the absorption edge with temperature is attributed to strongly temperature-dependent multiphonon absorption. While TBC hemispherical transmittance beyond the absorption edge can be predicted by a simple exponential decrease with thickness, below the absorption edge, typical TBC thicknesses are well below the thickness range where a simple exponential decrease in hemispherical transmittance with TBC thickness is expected. [Correction added after online publication August 11, 2009: "edge to a shorter wavelengths" has been updated as edge to shorter wavelengths."

In situ XAFS and micro-XAFS studies on LiNi 0.8Co 0.15Al 0.05O 2 cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Nonaka, T.; Okuda, C.; Seno, Y.; Nakano, H.; Koumoto, K.; Ukyo, Y.

We have applied in situ X-ray absorption fine structure (XAFS) and in situ micro-XAFS techniques to study LiNi 0.8Co 0.15Al 0.05O 2 cathode materials in Li-ion coin cells that show various levels of capacity fading: fresh cell, cycle tested cell and aging tested cell. The change in the oxidation state and local structure of Ni and Co during charge has been investigated. Ni and Co K-edge X-ray absorption near edge structure (XANES) show that the Ni oxidation state is converted from Ni 3+ to Ni 4+ upon charging, whereas the Co oxidation state hardly changes. Ni K-edge extended X-ray absorption fine structure (EXAFS) reveals that the Jahn-Teller distorted NiO 6 octahedron turns into the symmetric octahedron upon charging, which is consistent with the change in the Ni oxidation state. Ni K-edge micro-XANES show that the oxidation of Ni proceeds homogeneously in a grain of LiNi 0.8Co 0.15Al 0.05O 2 within the special resolution of ∼2 μm, and proceeds independently of the grain size. All the behaviors of Ni and Co observed in these experiments for the fresh cell remain unchanged after the capacity fade is induced by cycle tests or aging tests, which demonstrates the considerable stability of the LiNi 0.8Co 0.15Al 0.05O 2 cathode material.

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

PubMed

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

2013-08-07

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

Local 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.

Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

DTIC Science & Technology

2013-01-01

health risk. In addition Pb corrosion products may be sinks for other metals such as chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn). These...Vanadium K-Edge X-ray Absorption Near-Edge Structure Interpretation: Application to the Speciation of Vanadium in Oxide Phases from Steel Slag ’, Journal

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

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

DOE PAGES

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

2017-12-29

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

Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

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

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

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

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

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.

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

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

USGS Publications Warehouse

Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

2014-01-01

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3·5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm−1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe2+/[Fe2+ + Fe3+] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

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.

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

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

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.

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.

The disclosed transformation of pre-sputtered Ti films into nanoparticles via controlled thermal oxidation

NASA Astrophysics Data System (ADS)

Awad, M. A.; Raaif, M.

2018-05-01

Nanoparticles of TiO2 were successfully prepared from pre-sputtered Ti films using the controlled thermal oxidation. The effect of oxidation temperature on structural, morphological and optical properties in addition to photocatalysis activity of the sputtered films was tested and explained. Analysis of XRD and EDAX elucidated the enhancement in crystallization and oxygen content with the increase of oxidation temperature. SEM depicted the formation of very fine nanoparticles with no specific border on the films oxidized at 550 and 600 °C, whilst crystallites with larger size of approximately from 16 to 23 nm have been observed for the film oxidized at 650 °C. Both optical transmission and refractive index were increased with increasing the oxidation temperature. A red shift in the absorption edge was obtained for the films oxidized at 650 °C compared to that oxidized at 600 °C. The photocatalysis tests demonstrated the priority of 600 °C nanoparticle films to decompose methyl orange (MO) more than 650 °C treated film.

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

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

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.

X-ray Absorption Spectroscopic and Theoretical Studies on (L)2[Cu2(S2)n]2+ Complexes: Disulfide Versus Disulfide(•1−) Bonding

PubMed Central

Sarangi, Ritimukta; York, John T.; Helton, Matthew E.; Fujisawa, Kiyoshi; Karlin, Kenneth D.; Tolman, William B.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2008-01-01

Cu K-, L- and S K-edge X-ray absorption spectroscopic (XAS) data have been combined with density functional theory (DFT) calculations on [{(TMPA)Cu}2S2](ClO4)2 (1), [{Cu[HB(3,5-Pri2pz)3]}2(S2)] (2) and [{(TMEDA)Cu}2(S2)2](OTf)2 (3) to obtain a quantitative description of their ground state wavefunctions. The Cu L-edge intensities give 63% and 37% Cu d-character in the ground state of 1 and 2, respectively while the S K-pre-edge intensities reflect 20% and 48% S character in their ground states. These data indicate a more than two-fold increase in the total disulfide bonding character in 2 relative to 1. The increase in the number of Cu-S bonds in 2 (µ-η2:η2 S22− bridge) compared to 1 ((µ-η1:η1 S22− bridge), dominantly determines the large increase in covalency and Cu-disulfide bond strength in 2. Cu K- and L- and S K-pre-edge energy positions directly demonstrate the CuII/(S2−)2 nature of 3. The two disulfide(•1−)’s in 3 undergo strong bonding interactions which destabilize the resultant filled antibonding π* orbitals of the (S2−)2 fragment relative to the Cu 3d levels. This leads to an inverted bonding scheme in 3 with dominantly ligand based holes in its ground state, consistent with its description as a dicopper(II)-bis-disulfide(•1−) complex. PMID:18076173

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

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

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

2007-02-02

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

Heterostructured nanohybrid of zinc oxide-montmorillonite clay.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Hwang, Sung-Ho; Yang, Jae Hun; Choy, Jin-Ho

2006-02-02

We have synthesized heterostructured zinc oxide-aluminosilicate nanohybrids through a hydrothermal reaction between the colloidal suspension of exfoliated montmorillonite nanosheets and the sol solution of zinc acetate. According to X-ray diffraction, N2 adsorption-desorption isotherm, and field emission-scanning electron microscopic analyses, it was found that the intercalation of zinc oxide nanoparticles expands the basal spacing of the host montmorillonite clay, and the crystallites of the nanohybrids are assembled to form a house-of-cards structure. From UV-vis spectroscopic investigation, it becomes certain that calcined nanohybrid contains two kinds of the zinc oxide species in the interlayer space of host lattice and in mesopores formed by the house-of-cards type stacking of the crystallites. Zn K-edge X-ray absorption near-edge structure/extended X-ray absorption fine structure analyses clearly demonstrate that guest species in the nanohybrids exist as nanocrystalline zinc oxides with wurzite-type structure.

Resonant soft X-ray scattering on protein solutions

NASA Astrophysics Data System (ADS)

Ye, Dan; Le, Thinh; Wang, Cheng; Zwart, Peter; Gomez, Esther; Gomez, Enrique

Protein structure is crucial for biological function, such that characterizing protein folding and packing is important for the design of therapeutics and enzymes. We propose resonant soft X-ray scattering (RSOXS) as an approach to study proteins and other biological assemblies in solution. Calculations of the scattering contrast suggest that soft X-ray scattering is more sensitive than hard X-ray scattering, because of contrast generated at the absorption edges of constituent elements such as carbon, nitrogen and oxygen. We have examined the structure of bovine serum albumin (BSA) in solution by RSOXS. We find that by varying incident X-ray energies, we are able to achieve higher scattering contrast near the absorption edge. From our RSOXS scattering result we are able to reconstruct the structure of BSA in 3D. These RSOXS results also agree with hard X-ray experiments, including crystallographic data. Our study demonstrates the potential of RSOXS for studying protein structure in solution.

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.

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

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.

Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence.

PubMed

Cruz, Carlos M; Márquez, Irene R; Mariz, Inês F A; Blanco, Victor; Sánchez-Sánchez, Carlos; Sobrado, Jesús M; Martín-Gago, José A; Cuerva, Juan M; Maçôas, Ermelinda; Campaña, Araceli G

2018-04-28

Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects that promote the distortion of the otherwise planar lattice. The edge defects are an aromatic saddle-shaped ketone unit and a [5]carbohelicene moiety. This system is shown to combine two-photon absorption and circularly polarized luminescence and a remarkably long emission lifetime of 21.5 ns. The [5]helicene is responsible for the chiroptical activity while the push-pull geometry and the extended network of sp 2 carbons are factors favoring the nonlinear absorption. Electronic structure theoretical calculations support the interpretation of the results.

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.

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

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 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. Electronic supplementary information (ESI) available: The deconvoluted reference spectra are given in ESI Fig. 1-9. See DOI: 10.1039/c4nr07051h

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.

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.

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

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

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

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

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

DOE PAGES

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

2017-05-30

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

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.

Effect of substrates and thickness on optical properties in atomic layer deposition grown ZnO thin films

NASA Astrophysics Data System (ADS)

Pal, Dipayan; Singhal, Jaya; Mathur, Aakash; Singh, Ajaib; Dutta, Surjendu; Zollner, Stefan; Chattopadhyay, Sudeshna

2017-11-01

Atomic Layer Deposition technique was used to grow high quality, very low roughness, crystalline, Zinc Oxide (ZnO) thin films on silicon (Si) and fused quartz (SiO2) substrates to study the optical properties. Spectroscopic ellipsometry results of ZnO/Si system, staggered type-II quantum well, demonstrate that there is a significant drop in the magnitudes of both the real and imaginary parts of complex dielectric constants and in near-band gap absorption along with a blue shift of the absorption edge with decreasing film thickness at and below ∼20 nm. Conversely, UV-vis absorption spectroscopy of ZnO/SiO2, thin type-I quantum well, consisting of a narrower-band gap semiconductor grown on a wider-band gap (insulator) substrate, shows the similar thickness dependent blue-shift of the absorption edge but with an increase in the magnitude of near-band gap absorption with decreasing film thickness. Thickness dependent blue shift, energy vs. 1/d2, in two different systems, ZnO/Si and ZnO/SiO2, show a difference in their slopes. The observed phenomena can be consistently explained by the corresponding exciton (or carrier/s) deconfinement and confinement effects at the ZnO/Si and ZnO/SiO2 interface respectively, where Tanguy-Elliott amplitude pre-factor plays the key role through the electron-hole overlap factor at the interface.

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.

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.

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.

Stoichiometry of mercury-thiol complexes on bacterial cell envelopes

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

Mishra, Bhoopesh; Shoenfelt, Elizabeth; Yu, Qiang

We have examined the speciation of Hg(II) complexed with intact cell suspensions (1013 cells L- 1) of Bacillus subtilis, a common gram-positive soil bacterium, Shewanella oneidensis MR-1, a facultative gram-negative aquatic organism, and Geobacter sulfurreducens, a gram-negative anaerobic bacterium capable of Hg-methylation at Hg(II) loadings spanning four orders of magnitude (120 nM to 350 μM) at pH 5.5 (± 0.2). The coordination environments of Hg on bacterial cells were analyzed using synchrotron based X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy at the Hg LIII edge. The abundance of thiols on intact cells wasmore » determined by a fluorescence-spectroscopy based method using a soluble bromobimane, monobromo(trimethylammonio)bimane (qBBr) to block thiol sites, and potentiometric titrations of biomass with and without qBBr treatment. The chemical forms of S on intact bacterial cells were determined using S k-edge XANES spectroscopy.« less

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

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

DOE PAGES

Kroll, Thomas; Kern, Jan; Kubin, Markus; ...

2016-09-19

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. But, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. We compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based onmore » self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. Lastly, we show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements.« less

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

PubMed Central

Kroll, Thomas; Kern, Jan; Kubin, Markus; Ratner, Daniel; Gul, Sheraz; Fuller, Franklin D.; Löchel, Heike; Krzywinski, Jacek; Lutman, Alberto; Ding, Yuantao; Dakovski, Georgi L.; Moeller, Stefan; Turner, Joshua J.; Alonso-Mori, Roberto; Nordlund, Dennis L.; Rehanek, Jens; Weniger, Christian; Firsov, Alexander; Brzhezinskaya, Maria; Chatterjee, Ruchira; Lassalle-Kaiser, Benedikt; Sierra, Raymond G.; Laksmono, Hartawan; Hill, Ethan; Borovik, Andrew; Erko, Alexei; Föhlisch, Alexander; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe; Bergmann, Uwe

2016-01-01

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. PMID:27828320

Linear and Nonlinear Optical Properties of Spherical Quantum Dots: Effects of Hydrogenic Impurity and Conduction Band Non-Parabolicity

NASA Astrophysics Data System (ADS)

Rezaei, G.; Vaseghi, B.; Doostimotlagh, N. A.

2012-03-01

Simultaneous effects of an on-center hydrogenic impurity and band edge non-parabolicity on intersubband optical absorption coefficients and refractive index changes of a typical GaAs/AlxGa1-x As spherical quantum dot are theoretically investigated, using the Luttinger—Kohn effective mass equation. So, electronic structure and optical properties of the system are studied by means of the matrix diagonalization technique and compact density matrix approach, respectively. Finally, effects of an impurity, band edge non-parabolicity, incident light intensity and the dot size on the linear, the third-order nonlinear and the total optical absorption coefficients and refractive index changes are investigated. Our results indicate that, the magnitudes of these optical quantities increase and their peaks shift to higher energies as the influences of the impurity and the band edge non-parabolicity are considered. Moreover, incident light intensity and the dot size have considerable effects on the optical absorption coefficients and refractive index changes.

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.

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.

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE PAGES

Baker, Michael L.; Mara, Michael W.; Yan, James J.; ...

2017-02-09

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

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

Baker, Michael L.; Mara, Michael W.; Yan, James J.

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

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.

Electronic structure differences between H(2)-, Fe-, Co-, and Cu-phthalocyanine highly oriented thin films observed using NEXAFS spectroscopy.

PubMed

Willey, T M; Bagge-Hansen, M; Lee, J R I; Call, R; Landt, L; van Buuren, T; Colesniuc, C; Monton, C; Valmianski, I; Schuller, Ivan K

2013-07-21

Phthalocyanines, a class of macrocyclic, square planar molecules, are extensively studied as semiconductor materials for chemical sensors, dye-sensitized solar cells, and other applications. In this study, we use angular dependent near-edge x-ray absorption fine structure (NEXAFS) spectroscopy as a quantitative probe of the orientation and electronic structure of H2-, Fe-, Co-, and Cu-phthalocyanine molecular thin films. NEXAFS measurements at both the carbon and nitrogen K-edges reveal that phthalocyanine films deposited on sapphire have upright molecular orientations, while films up to 50 nm thick deposited on gold substrates contain prostrate molecules. Although great similarity is observed in the carbon and nitrogen K-edge NEXAFS spectra recorded for the films composed of prostrate molecules, the H2-phthalocyanine exhibits the cleanest angular dependence due to its purely out-of-plane π* resonances at the absorption onset. In contrast, organometallic-phthalocyanine nitrogen K-edges have a small in-plane resonance superimposed on this π* region that is due to a transition into molecular orbitals interacting with the 3dx(2)-y(2) empty state. NEXAFS spectra recorded at the metal L-edges for the prostrate films reveal dramatic variations in the angular dependence of specific resonances for the Cu-phthalocyanines compared with the Fe-, and Co-phthalocyanines. The Cu L3,2 edge exhibits a strong in-plane resonance, attributed to its b1g empty state with dx(2)-y(2) character at the Cu center. Conversely, the Fe- and Co- phthalocyanine L3,2 edges have strong out-of-plane resonances; these are attributed to transitions into not only b1g (dz(2)) but also eg states with dxz and dyz character at the metal center.

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

XAS Studies of Arsenic in the Environment

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

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

XAFS Study of Molten ZrCl4 in LiCl-KCl Eutectic

NASA Astrophysics Data System (ADS)

Okamoto, Yoshihiro; Motohashi, Haruhiko

2002-05-01

The local structure of motlen ZrCl4 in LiCl-KCl eutectic was investigated by using an X-ray absorption fine structure (XAFS) of the Zr K-absorption edge. The nearest Zr4+-Cl- distance and coordination number from the curve fitting analysis were (2.51±0.02) Å and 5.9±0.6, respectively. These suggest that a 6-fold coordination (ZrCl6)2- is predominant in the molten mixture.

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

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

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

PubMed

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

2016-04-05

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

X-ray Absorption and Emission Spectroscopic Studies of [L2Fe2S2]n Model Complexes: Implications for the Experimental Evaluation of Redox States in Iron–Sulfur Clusters

PubMed Central

2016-01-01

Herein, a systematic study of [L2Fe2S2]n model complexes (where L = bis(benzimidazolato) and n = 2-, 3-, 4-) has been carried out using iron and sulfur K-edge X-ray absorption (XAS) and iron Kβ and valence-to-core X-ray emission spectroscopies (XES). These data are used as a test set to evaluate the relative strengths and weaknesses of X-ray core level spectroscopies in assessing redox changes in iron–sulfur clusters. The results are correlated to density functional theory (DFT) calculations of the spectra in order to further support the quantitative information that can be extracted from the experimental data. It is demonstrated that due to canceling effects of covalency and spin state, the information that can be extracted from Fe Kβ XES mainlines is limited. However, a careful analysis of the Fe K-edge XAS data shows that localized valence vs delocalized valence species may be differentiated on the basis of the pre-edge and K-edge energies. These findings are then applied to existing literature Fe K-edge XAS data on the iron protein, P-cluster, and FeMoco sites of nitrogenase. The ability to assess the extent of delocalization in the iron protein vs the P-cluster is highlighted. In addition, possible charge states for FeMoco on the basis of Fe K-edge XAS data are discussed. This study provides an important reference for future X-ray spectroscopic studies of iron–sulfur clusters. PMID:27097289

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

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.

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.

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.

Bandgap behavior and singularity of the domain-induced light scattering through the pressure-induced ferroelectric transition in relaxor ferroelectric AxBa1-xNb2O6 (A: Sr,Ca)

NASA Astrophysics Data System (ADS)

Ruiz-Fuertes, J.; Gomis, O.; Segura, A.; Bettinelli, M.; Burianek, M.; Mühlberg, M.

2018-01-01

In this letter, we have investigated the electronic structure of AxBa1-xNb2O6 relaxor ferroelectrics on the basis of optical absorption spectroscopy in unpoled single crystals with A = Sr and Ca under high pressure. The direct character of the fundamental transition could be established by fitting Urbach's rule to the photon energy dependence of the absorption edge yielding bandgaps of 3.44(1) eV and 3.57(1) eV for A = Sr and Ca, respectively. The light scattering by ferroelectric domains in the pre-edge spectral range has been studied as a function of composition and pressure. After confirming with x-ray diffraction the occurrence of the previously observed ferroelectric to paraelelectric phase transition at 4 GPa, the light scattering produced by micro- and nano-ferroelectric domains at 3.3 eV in Ca0.28Ba0.72Nb2O6 has been probed. The direct bandgap remains virtually constant under compression with a drop of only 0.01 eV around the phase transition. Interestingly, we have also found that light scattering by the polar nanoregions in the paraelectric phase is comparable to the dispersion due to ferroelectric microdomains in the ferroelectric state. Finally, we have obtained that the bulk modulus of the ferroelectric phase of Ca0.28Ba0.72Nb2O6 is B0 = 222(9) GPa.

Probing the electronic and local structural changes across the pressure-induced insulator-to-metal transition in VO2

NASA Astrophysics Data System (ADS)

Marini, C.; Bendele, M.; Joseph, B.; Kantor, I.; Mitrano, M.; Mathon, O.; Baldini, M.; Malavasi, L.; Pascarelli, S.; Postorino, P.

2014-11-01

Local and electronic structures of vanadium in \\text{VO}2 are studied across the high-pressure insulator-to-metal (IMT) transition using V K-edge x-ray absorption spectroscopy. Unlike the temperature-induced IMT, pressure-induced metallization leads to only subtle changes in the V K-edge prepeak structure, indicating a different mechanism involving smaller electronic spectral weight transfer close to the chemical potential. Intriguingly, upon application of the hydrostatic pressure, the electronic structure begins to show substantial changes well before the occurrence of the IMT and the associated structural transition to an anisotropic compression of the monoclinic metallic phase.

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.

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.

The Amyloid-β Peptide of Alzheimer’s Disease Binds CuI in a Linear Bis-His Coordination Environment: Insight into a Possible Neuroprotective Mechanism for the Amyloid-β Peptide

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

Shearer, J.; Szalai, V

Oxidative stress has been suggested to contribute to neuronal apoptosis associated with Alzheimer's disease (AD). Copper may participate in oxidative stress through redox-cycling between its +2 and +1 oxidation states to generate reactive oxygen species (ROS). In vitro, copper binds to the amyloid-? peptide of AD, and in vivo, copper is associated with amyloid plaques characteristic of AD. As a result, the A?CuI complex may be a critical reactant involved in ROS associated with AD etiology. To characterize the A?CuI complex, we have pursued X-ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopy of A?CuII and A?CuI (produced by ascorbatemore » reduction of A?CuII). The A?CuII complex Cu K-edge XAS spectrum is indicative of a square-planar CuII center with mixed N/O ligation. Multiple scattering analysis of the extended X-ray absorption fine structure (EXAFS) data for A?CuII indicates that two of the ligands are imidazole groups of histidine ligands, indicating a (NIm)2(N/O)2 CuII ligation sphere for A?CuII. After reduction of the A?CuII complex with ascorbate, the edge region decreases in energy by 4 eV. The X-ray absorption near-edge spectrum region of A?CuI displays an intense pre-edge feature at 8984.1(2) eV. EXAFS data fitting yielded a two-coordinate geometry, with two imidazole ligands coordinated to CuI at 1.877(2) A in a linear geometry. Ascorbate reduction of A?CuII under inert atmosphere and subsequent air oxidation of A?CuI to regenerate A?CuII was monitored by low-temperature EPR spectroscopy. Slow reappearance of the A?CuII EPR signal indicates that O2 oxidation of the A?CuI complex is kinetically sluggish and A? damage is occurring following reoxidation of A?CuI by O2. Together, these results lead us to hypothesize that CuI is ligated by His13 and His14 in a linear coordination environment in ??, that A? may be playing a neuroprotective role, and that metal-mediated oxidative damage of A? occurs over multiple redox cycles.« less

Pinned orbital moments in uncompensated antiferromagnetic Co doped ZnO

NASA Astrophysics Data System (ADS)

Buchner, Martin; Henne, Bastian; Ney, Verena; Lumetzberger, Julia; Wilhelm, Fabrice; Rogalev, Andrei; Hen, Amir; Ney, Andreas

2018-05-01

Low temperature Co K-edge x-ray magnetic circular dichroism spectra at different field cooling conditions were recorded to study the imprinted magnetization in antiferromagnetic (AFM) Co doped ZnO (Co:ZnO) films which manifests itself in a vertical exchange bias effect. Co:ZnO films with 50% and 60% doping concentrations were investigated to provide a high degree of pinned magnetic moments. The measurements reveal a change at the main absorption energy of the spectra, while the signal obtained at the pre-edge stays unaffected by the cooling conditions. Therefore, the pinned uncompensated AFM moments, resulting in an imprinted magnetization, are predominantly of orbital character and are independent of ferromagnetic layers.

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.

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.

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

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).

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.

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.

Structural, electronic and photocatalytic properties of atomic defective BiI3 monolayers

NASA Astrophysics Data System (ADS)

Yan, Huang; Ziyu, Hu; Xu, Gong; Xiaohong, Shao

2018-01-01

The structural, electronic and photocatalytic properties of five vacancy-containing 2D BiI3 monolayers are investigated by the first-principle calculations. The electronic structures show that the five structures are stable and have comparable binding energies to that of the pristine BiI3 monolayer, and the defects can tune the band gaps. Optical spectra indicate that the five structures retain high absorption capacity for visible light. The spin-orbit coupling (SOC) effect is found to play an important role in the band edge of defective structures, and the VBi and VBi-I3 defective BiI3 monolayers can make absolute band edges straddle water redox potentials more easily.

Electronic structure, magnetism, and optical properties of Fe2SiO4 fayalite at ambient and high pressures: A GGA+U study

NASA Astrophysics Data System (ADS)

Jiang, Xuefan; Guo, G. Y.

2004-04-01

The electronic structure, magnetism, and optical properties of Fe2SiO4 fayalite, the iron-rich end member of the olivine-type silicate, one of the most abundant minerals in Earth’s upper mantle, have been studied by density-functional theory within the generalized gradient approximation (GGA) with the on-site Coulomb energy U=4.5 eV taken into account (GGA+U). The stable insulating antiferromagnetic solution with an energy gap ˜1.49 eV and a spin magnetic moment of 3.65μB and an orbital magnetic moment of 0.044μB per iron atom is obtained. It is found that the gap opening in this fayalite results mainly from the strong on-site Coulomb interaction on the iron atoms. In this band structure, the top of valence bands consists mainly of the 3d orbitals of Fe2 atoms, and the bottom of the conduction bands is mainly composed of the 3d orbitals of Fe1 atoms. Therefore, since the electronic transition from the Fe2 3d to Fe1 3d states is weak, significant electronic transitions would appear only about 1 eV above the absorption edge when Fe-O orbitals are involved in the final states. In addition, our band-structure calculations can explain the observed phenomena including redshift near the absorption edge and the decrease of the electrical resistivity of Fe2SiO4 upon compression. The calculated Fe p partial density of states agree well with Fe K-edge x-ray absorption spectrum. The calculated lattice constants and atomic coordinates for Fe2SiO4 fayalite in orthorhombic structure are in good agreement with experiments.

Non-invasive localization of organic matter in soil aggregates using SR-μCT

NASA Astrophysics Data System (ADS)

Peth, Stephan; Mordhorst, Anneka; Chenu, Claire; Uteau Puschmann, Daniel; Garnier, Patricia; Nunan, Naoise; Pot, Valerie; Beckmann, Felix; Ogurreck, Malte

2014-05-01

Knowledge of the location of soil organic matter (SOM) and its spatial association to soil structure is an important step in improving modeling approaches for simulating organic matter turnover processes. Advanced models for carbon mineralization are able to account for the 3D distribution of SOM which is assumed to influence mineralisation. However, their application is still limited by the fact that no method exists to non-invasively determine the 3D spatial distribution of SOM in structured soils. SR-based X-ray microtomography (SR-µCT) is an advanced and promising tool in gaining knowledge on the 3-dimensional organization of soil phases (minerals, organic matter, water, air) which on a voxel level could be implemented into spatially explicit models. However, since the contrast of linear attenuation coefficients of soil organic matter on the one hand and mineral components and water on the other hand are relatively low, especially when materials are finely dispersed, organic matter within the soil pore space is often not resolved in ordinary X-ray absorption contrast imaging. To circumvent this problem we have developed a staining procedure for organic matter using Osmium-tetroxide since Osmium is an element with an absorption edge at a higher X-ray energy level. Osmium is known from transmission electron microscopy analysis (TEM) to stain organic matter specifically and irreversibly while having an absorption edge at approximately 74 keV. We report on the application of a novel Osmium vapor staining method to analyze differences in organic matter content and identify small scale spatial distribution of SOM in soil aggregates. To achieve this we have taken soil aggregate samples (6-8 mm across) obtained from arable soils differing in soil management. Aggregate samples were investigated by synchrotron-based X-ray microtomography (SR-µCT) after staining the sample with Osmium-tetroxide (OsO4) vapor. We utilized the monochromatic X-ray beam to locate osmium bound to SOM in the stained soil aggregate samples by scanning the aggregates at different photon energies: 30 keV at which the attenuation contrast is optimal for distinguishing other soil constituents, 70 keV (below the absorption of osmium) and 78 keV (above the absorption edge of osmium). The results suggest that particulate organic matter, which was not visibly by scanning samples at energy levels optimal for resolving soil structure (30 keV), was identified after osmium staining and scanning the samples at energy levels just below (70 keV) and above (78 keV) the absorption edge of Osmium. Subtracting the images below from the images above the osmium edged we were able to isolate stained particulate organic matter which otherwise would have been wrongly interpreted as pore space without staining. Combining both pore space and organic matter distribution we are able to investigate the association of SOM with soil structure.

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.

Structural, optical, physical and electrical properties of V2O5.SrO.B2O3 glasses.

PubMed

Sindhu, S; Sanghi, S; Agarwal, A; Seth, V P; Kishore, N

2006-05-01

The present work aims to study the structure and variation of optical band gap, density and dc electrical conductivity in vanadium strontium borate glasses. The glass systems xV2O5.(40-x)SrO.60B2O3 and xV2O5.(60-x)B2O3.40SrO with x varying from 0 to 20 mol% were prepared by normal melt quench technique. Structural studies were made by recording IR transmission spectra. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. The position of absorption edge and hence the value of the optical band gap was found to depend on the semiconducting glass composition. The absorption in these glasses is believed to be associated with indirect transitions. The origin of Urbach energy is associated with the phonon-assisted indirect transitions. The change in both density and molar volume was discussed in terms of the structural modifications that take place in the glass matrix on addition of V2O5. dc conductivity of the glass systems is also reported. The change of conductivity and activation energy with composition indicates that the conduction process varies from ionic to polaronic one.

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).

Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence† †Electronic supplementary information (ESI) available: General details, synthesis and spectroscopy data of new compounds. Experimental details on optical, chiroptical, electrochemical and on-surface measurements. Crystal data and structure refinement of compounds 1, and 6. Further details on theoretical calculations and Cartesian coordinates of computed structures. VT-H1NMR, 2D-NMR and HRMS spectra of 1. CCDC 1561552 and 1561553. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00427g

PubMed Central

Cruz, Carlos M.; Márquez, Irene R.; Mariz, Inês F. A.; Blanco, Victor; Sánchez-Sánchez, Carlos; Sobrado, Jesús M.; Martín-Gago, José A.; Cuerva, Juan M.

2018-01-01

Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects that promote the distortion of the otherwise planar lattice. The edge defects are an aromatic saddle-shaped ketone unit and a [5]carbohelicene moiety. This system is shown to combine two-photon absorption and circularly polarized luminescence and a remarkably long emission lifetime of 21.5 ns. The [5]helicene is responsible for the chiroptical activity while the push–pull geometry and the extended network of sp2 carbons are factors favoring the nonlinear absorption. Electronic structure theoretical calculations support the interpretation of the results. PMID:29780523

Resonant magnetic scattering of polarized soft x rays

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

Sacchi, M.; Hague, C.F.; Gullikson, E.M.

1997-04-01

Magnetic effects on X-ray scattering (Bragg diffraction, specular reflectivity or diffuse scattering) are a well known phenomenon, and they also represent a powerful tool for investigating magnetic materials since it was shown that they are strongly enhanced when the photon energy is tuned across an absorption edge (resonant process). The resonant enhancement of the magnetic scattering has mainly been investigated at high photon energies, in order to match the Bragg law for the typical lattice spacings of crystals. In the soft X-ray range, even larger effects are expected, working for instance at the 2p edges of transition metals of themore » first row or at the 3d edges of rare earths (300-1500 eV), but the corresponding long wavelengths prevent the use of single crystals. Two approaches have been recently adopted in this energy range: (i) the study of the Bragg diffraction from artificial structures of appropriate 2d spacing; (ii) the analysis of the specular reflectivity, which contains analogous information but has no constraints related to the lattice spacing. Both approaches have their own specific advantages: for instance, working under Bragg conditions provides information about the (magnetic) periodicity in ordered structures, while resonant reflectivity can easily be related to electronic properties and absorption spectra. An important aspect common to all the resonant X-ray scattering techniques is the element selectivity inherent to the fact of working at a specific absorption edge: under these conditions, X-ray scattering becomes in fact a spectroscopy. Results are presented for films of iron and cobalt.« less

Experimental and theoretical XANES of CdSxSe1-x nanostructures

NASA Astrophysics Data System (ADS)

Yiu, Y. M.; Murphy, M. W.; Liu, L.; Hu, Y.; Sham, T. K.

2014-03-01

The morphology and electronic properties of the CdSxSe1-x nanostructures with varying alloy compositions have been acquired experimentally by X-ray Absorption Near-Edge Structures (XANES) at the Cd, Se and S K-edge and L3,2-edges. The theoretical XANES spectra have been calculated using the density functional approach. It is found that the optical band-gap emission of these CdSxSe1-x nano-ribbons can be tuned to the range between that of pure CdS (2.43 eV) and CdSe (1.74 eV) by changing the S and Se ratio. This gradual shift in (optical and structural) properties from CdS character to CdSe character is also seen in the electronic structures. The densities of states and band structures show that with the addition of Se replacing S in CdS, the band gap shrinks. The K and L3,2 edges of Cd, Se, and S of the XANES structures of both the CdS and CdSe in B4 (wurtzite) and B3 (cubic zinc-blende) structures have been calculated and compared.

Local surrounding of Mn in LaMn 1-xCo xO 3 compounds by means of EXAFS on Mn-K

NASA Astrophysics Data System (ADS)

Procházka, Vít; Sikora, Marcin; Kapusta, Czeslaw; Štěpánková, Helena; Chlan, Vojtěch; Knížek, Karel; Jirák, Zdeněk

2010-05-01

A systematic study of LaMn 1-xCo xO 3 perovskite series by means of X-ray absorption spectroscopy in the extended X-ray absorption fine structure (EXAFS) range of the K-absorption edge of Mn is reported. The Mn-K edge absorption measurements in the EXAFS region were performed to study the local surrounding of Mn ions. Polycrystalline powder samples of LaMn 1-xCo xO 3 ( x=0, 0.02; 0.2; 0.4; 0.5; 0.6; 0.8) prepared by solid-state reaction were used. The EXAFS spectra were analyzed with the FEFF8 computer program. The Mn-O distances of Mn to the nearest oxygen surroundings were evaluated for the samples in the series and compared with the Co-O distances obtained by EXAFS in V. Procházka et al., JMMM 310 (2007) 197 and with results of X-ray powder diffraction in C. Autret, J. Phys. Condens. Matter 17 (2005) 1601.

On Local Ionization Equilibrium and Disk Winds in QSOs

NASA Astrophysics Data System (ADS)

Pereyra, Nicolas A.

2014-11-01

We present theoretical C IV λλ1548,1550 absorption line profiles for QSOs calculated assuming the accretion disk wind (ADW) scenario. The results suggest that the multiple absorption troughs seen in many QSOs may be due to the discontinuities in the ion balance of the wind (caused by X-rays), rather than discontinuities in the density/velocity structure. The profiles are calculated from a 2.5-dimensional time-dependent hydrodynamic simulation of a line-driven disk wind for a typical QSO black hole mass, a typical QSO luminosity, and for a standard Shakura-Sunyaev disk. We include the effects of ionizing X-rays originating from within the inner disk radius by assuming that the wind is shielded from the X-rays from a certain viewing angle up to 90° ("edge on"). In the shielded region, we assume constant ionization equilibrium, and thus constant line-force parameters. In the non-shielded region, we assume that both the line-force and the C IV populations are nonexistent. The model can account for P-Cygni absorption troughs (produced at edge on viewing angles), multiple absorption troughs (produced at viewing angles close to the angle that separates the shielded region and the non-shielded region), and for detached absorption troughs (produced at an angle in between the first two absorption line types); that is, the model can account for the general types of broad absorption lines seen in QSOs as a viewing angle effect. The steady nature of ADWs, in turn, may account for the steady nature of the absorption structure observed in multiple-trough broad absorption line QSOs. The model parameters are M bh = 109 M ⊙ and L disk = 1047 erg s-1.

Structure of CdTe nanoparticles in glass

NASA Astrophysics Data System (ADS)

Hayes, T. M.; Nagpal, Swati; Persans, P. D.

2000-03-01

Optical long-pass wavelength filters are generally made by growing small crystallites of appropriate semiconductors in a transparent glass matrix. Depending on the semiconductor, these systems are candidates for interesting and important nonlinear optical switching applications. The structure of these nanocrystals has been shown to be a valuable indicator of the chemical and thermodynamic processes during crystallite growth and dissolution. We have used x-ray absorption spectroscopy to study the structure of the crystallites produced during heat treatment of filter glasses containing Cd and Te and producing optical absorption edges at the band gap of bulk CdTe. The results will be discussed.

Synchrotron X-ray spectroscopic investigations of an Nb-bearing silicate melt in contact with an aqueous fluid

NASA Astrophysics Data System (ADS)

Mayanovic, R. A.; Anderson, A. J.; Bassett, W. A.; Chou, I.

2006-05-01

Understanding the structural properties of trace elements in hydrous silicate melts in contact with a hydrothermal fluid is fundamentally important for a better assessment of the role of such elements in silicate melts being subjected to hydrothermal processes. We describe the use of synchrotron x-ray microprobe techniques and the modified hydrothermal diamond-anvil cell for in-situ spectroscopic analysis of individual phases of a silicate-melt/fluid system. Synchrotron X-ray fluorescence (XRF) and Nb K-edge X-ray absorption fine structure (XAFS) measurements were made on sectors ID20 and ID13 at the Advanced Photon Source, at the Argonne National Laboratory, on a Nb-bearing granitic glass in H2O and separately in a 1 M Na2CO3 aqueous solution at temperatures ranging from 25 to 880 °C and at up to 700 MPa of pressure. Individual phases of the Nb-glass/fluid system (at low temperatures) or the hydrous-silicate-melt/fluid system (at elevated temperatures) were probed using an X-ray beam focused to a diameter of 5 μm at the location of the sample. XRF analysis shows that the Nb partitions selectively from the hydrous silicate melt into the aqueous fluid at high temperatures in the Nb-glass/Na2CO3/H2O system but not so in the Nb-glass/H2O system. Analysis of XAFS spectra measured from the hydrous silicate melt phase of the Nb-glass/H2O sample in the 450 to 700 °C range shows that the first shell contains six oxygen atoms at a distance of ~1.98 Å. Our results suggest that reorganization of the silicate structure surrounding Nb occurs in the melt when compared to that of the starting glass. The X-ray absorption near edge structure (XANES) spectra show a pre-edge peak feature located at ~18995 eV that exhibits sharpening and becomes more intensified in the 450 to 700 °C range. Fitting of the Nb K-edge XANES spectra measured from the melt is accomplished using FEFF8.28 and an atomic model NbSi4O6-4(Na, K). The model is based on the structure of fresnoite (Ba2TiSi2O8), in which an NbO6 octahedron unit is substituted for the TiO5 unit, four Na and four K atoms are placed alternately on nearby Ba atom sites, and four Si atoms are arranged in a single plane intersecting the NbO6 unit. The results from fitting indicate that the local structure of Nb in the silicate melt is altered from its local structure in the quenched glass before heating and in the glass after heating in the diamond anvil cell. The importance of in situ analysis of melts and hydrothermal fluids at various temperatures and pressures is discussed in the context of our study.

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.

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.

Optical properties of truncated Au nanocages with different size and shape

NASA Astrophysics Data System (ADS)

Chen, Qin; Qi, Hong; Ren, Ya-Tao; Sun, Jian-Ping; Ruan, Li-Ming

2017-06-01

The hollow nanostructures are conducive to applications including drug delivery, energy storage and conversion, and catalysis. In the present work, a versatile type of Au nanoparticles, i.e. nanocage with hollow interior, was studied thoroughly. Simulation of the optical properties of nanocages with different sizes and shapes was presented, which is essential for tuning the localized surface plasmon resonance peak. The edge length, side length of triangle, and wall thickness were used as structural parameters of truncated Au nanocage. The dependence of absorption efficiency, resonant wavelength, and absorption quantum yield on the structural parameters were discussed. Meanwhile, the applications of absorption quantum yield in biomedical imaging and laser induced thermal therapy were investigated. It was found that the phenomenon of multipolar plasmon resonances exists on truncated Au nanocage. Furthermore, the electric field distribution at different resonant wavelengths was also investigated. It is found that the electromagnetic field corresponds to the dipolar mode in an individual nanocage is largely distributed at the corners. Whereas, the electromagnetic field corresponds to the multipolar region is mainly located in the internal corners and edges.

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

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

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

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.

Band-filling of solution-synthesized CdS nanowires.

PubMed

Puthussery, James; Lan, Aidong; Kosel, Thomas H; Kuno, Masaru

2008-02-01

The band edge optical characterization of solution-synthesized CdS nanowires (NWs) is described. Investigated wires are made through a solution-liquid-solid approach that entails the use of low-melting bimetallic catalyst particles to seed NW growth. Resulting diameters are approximately 14 nm, and lengths exceed 1 microm. Ensemble diameter distributions are approximately 13%, with corresponding intrawire diameter variations of approximately 5%. High-resolution transmission electron micrographs show that the wires are highly crystalline and have the wurtzite structure with growth along at least two directions: [0001] and [1010]. Band edge emission is observed with estimated quantum yields between approximately 0.05% and 1%. Complementary photoluminescence excitation spectra show structure consistent with the linear absorption. Carrier cooling dynamics are subsequently examined through ensemble lifetime and transient differential absorption measurements. The former reveals unexpectedly long band edge decays that extend beyond tens of nanoseconds. The latter indicates rapid intraband carrier cooling on time scales of 300-400 fs. Subsequent recovery at the band edge contains significant Auger contributions at high intensities which are usurped by other, possibly surface-related, carrier relaxation pathways at lower intensities. Furthermore, an unusual intensity-dependent transient broadening is seen, connected with these long decays. The effect likely stems from band-filling on the basis of an analysis of observed spectral shifts and line widths.

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

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.

XAS study of chromium in Li 2MSiO 4 (M=Mg, Zn)

NASA Astrophysics Data System (ADS)

Jousseaume, C.; Ribot, F.; Kahn-Harari, A.; Vivien, D.; Villain, F.

2003-01-01

X-ray absorption spectroscopy (XAS) investigations at the Cr K-edge on Cr:Li 2MSiO 4 (M=Mg, Zn) have been performed to understand the exceptionally long fluorescence lifetime of Cr IV. Previous work has shown the simultaneous presence of three oxidation states Cr IV, Cr V and Cr VI. X-ray absorption near edge structure measurements confirm that Cr in Li 2MSiO 4 (M=Mg, Zn) single crystals is in tetrahedral coordination. They also reveal that Cr VI is the dominant species in Li 2MgSiO 4, and that Li 2ZnSiO 4 contains more Cr V than Li 2MgSiO 4. The extended X-ray absorption fine structure spectra of Cr:Li 2MgSiO 4 single crystals recorded at the Cr K-edge, are fitted with two types of Cr environments: the first one corresponds to oxygen atoms at a mean distance of 1.68 Å and the second to oxygen atoms at a mean distance of 2.07 Å. This second environment is attributed to Cr III in the minor parasitic phase LiCr IIIO 2. The first environment corresponds to Cr that substitutes silicon in the Li 2MgSiO 4 lattice in the silicon site if the cations sizes are considered.

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.

Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p-Aminobenzoic Acid.

PubMed

Stevens, Joanna S; Gainar, Adrian; Suljoti, Edlira; Xiao, Jie; Golnak, Ronny; Aziz, Emad F; Schroeder, Sven L M

2015-05-04

Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO-LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. This provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute-solvent interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid

DOE PAGES

Stevens, Joanna S.; Gainar, Adrian; Suljoti, Edlira; ...

2015-03-18

Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs andmore » σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.« less

X-Ray Absorption Spectra of Amorphous Ices from GW Quasiparticle Calculation

NASA Astrophysics Data System (ADS)

Kong, Lingzhu; Car, Roberto

2013-03-01

We use a GW approach[2] to compute the x-ray absorption spectra of model low- and high-density amorphous ice structures(LDA and HDA)[3]. We include the structural effects of quantum zero point motion using colored-noise Langevin molecular dynamics[4]. The calculated spectra differences in the main and post edge region between LDA and HDA agree well with experimental observations. We attribute these differences to the presence of interstitial molecules within the first coordination shell range in HDA. This assignment is further supported by a calculation of the spectrum of ice VIII, a high-pressure structure that maximizes the number of interstitial molecules and, accordingly, shows a much weaker post-edge feature. We further rationalize the spectral similarity between HDA and liquid water, and between LDA and ice Ih in terms of the respective similarities in the H-bond network topology and bond angle distributions. Supported by grants DOE-DE-SC0005180, DOE DE-SC0008626 and NSF-CHE-0956500.

Effect of Co and O defects on ferromagnetism in Co-doped ZnO: An X-ray absorption spectroscopic investigation

NASA Astrophysics Data System (ADS)

Singhal, Rishi K.; Jakhar, Narendra; Samariya, A.; Dolia, S. N.; Kumar, Sudhish

2018-02-01

Understanding of origin of ferromagnetism in dilute magnetic oxides (DMO's) has become one of the most challenging research problems in condensed matter physics. Here we are reporting a detailed study of magnetic properties and electronic structure of two 5% Co-doped ZnO samples (the as-prepared sample Zn0.95Co0.05O and the hydrogenated sample Zn0.95Co0.05O:H). The as-prepared sample is found to be paramagnetic while through hydrogenation, we observed inducement of remarkable ferromagnetism in it. The H-mediated magnetic transition is accompanied by electronic structure modifications with no structural deviations. To get in-depth information into electronic structure correlations of the observed ferromagnetism, we have investigated their electronic properties in detail. For this purpose, we have employed the site-selective and element-sensitive X-ray-absorption spectroscopy (XAS) in the vicinity of the Cobalt L2,3 edge, the oxygen K edge, and the Zinc L3 edge using synchrotron radiation. The Co L2,3 edge spectra clearly show that Co dopants reside at the Zn sites for both these samples and that they are tetrahedrally coordinated with the ligand O atoms. Very minor changes are observed in the Zn L3 edge spectra. However, the O 1s edge spectra display dominant additional components in the ferromagnetic hydrogenated sample Zn0.95Co0.05O:H, not observed in the as-prepared non-magnetic sample Zn0.95Co0.05O. We conclude that the observed spectral features can be attributed to the presence of O vacancies and the hybridization of Co 3d states with O 2p vacancy states. These two factors together are likely to play important role in inducement of ferromagnetic ordering in this Co-doped ZnO system. However, which of these two weighs more in this mechanism, cannot be pinpointed and more studies are required in this regard.

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.

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.

Electronic states in oxidized NaxCoO2 as revealed by X-ray absorption spectroscopy coupled with ab initio calculation

NASA Astrophysics Data System (ADS)

Niwa, Hideharu; Higashiyama, Kazuyuki; Amaha, Kaoru; Kobayashi, Wataru; Moritomo, Yutaka

2018-04-01

Layered cobalt oxides are promising cathode materials for sodium ion secondary batteries (SIBs). By combined study of the X-ray absorption spectroscopy (XAS) around the O K-edge and ab initio calculation, we investigated the electronic state of the NaxCoO2 with different oxidization state, i.e, in O3-Na0.91CoO2 (CoO2-0.91) and P2-Na0.66CoO2 (CoO2-0.66). The O K-edge spectra in the pre-edge (529-536 eV) region shows significant change with oxidization of NaxCoO2. In O3-Na0.91CoO2, the spectra shows an intense band (B band) at 531 eV. In P2-Na0.66CoO2, the spectral weight of the B band increases and a new band (A band) appears at 530 eV. These spectral changes are qualitatively reproduced by the calculated partial density of states (pDOSs) of O3-NaCoO2 and P2-Na1/2CoO2. These results indicate that the electrons are partially removed from the O 2p state with oxidization of NaxCoO2.

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

Local structure and polarization resistance of Ce doped SrMnO{sub 3} using extended x-ray fine structure analysis

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

Ryu, Jiseung; Lee, Heesoo, E-mail: heesoo@pusan.ac.kr

2014-09-15

Changes to the local structure of Sr and Mn atoms in Sr{sub 1−x}Ce{sub x}MnO{sub 3} (SCM) according to increasing Ce content and the effect of the structural change on the polarization resistance of SCM were investigated. The reduction of manganese was confirmed by the absorption edge shift of the Mn K-edge toward lower energies. The noise of oscillation in extended X-ray absorption fine structure k{sup 3}χ data at Mn K-edge reveals the distortion of the local structure of Mn atoms, and the peak that indicates the bonding length of Mn-O, Sr/Ce, and -Mn decreased with the addition of Ce contentmore » in Fourier transformations of the Mn K-edge. The distortion of the local structure at Mn atoms was affected by the reduced manganese ions having larger ionic radii than Mn{sup 4+}. Meanwhile, few distortions of local atomic structures of Sr atoms occurred, and the average nearest neighboring distances of Sr-O and Sr-Mn are ∼2.13 Å and ∼2.95 Å, respectively. The average bonding lengths of the Ce-O and Ce-Mn increased because the ionic radius of substituted Ce ion with 12 coordination number is smaller than that of Sr ion, which leads the reduction of Mn ions and the distortion of local structure at the substituted A-site. Therefore, we reasoned that the distortion of the local atomic structure at Mn atoms in MnO{sub 6} and Ce atoms in A-site is one of the causes for interrupting oxygen ion transfers as a geometric factor, which results in an increase in the polarization resistance of SCM within the Ce composition range from 10 mol. % to 30 mol. %.« less

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

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

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« less

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

DOE PAGES

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.; ...

2016-11-30

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« less

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.

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.

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.

Optical band gap studies on lithium aluminum silicate glasses doped with Cr3+ ions

NASA Astrophysics Data System (ADS)

El-Diasty, Fouad; Abdel Wahab, Fathy A.; Abdel-Baki, Manal

2006-11-01

Lithium aluminum silicate glass system (LAS) implanted with chromium ions is prepared. The reflectance and transmittance measurements are used to determine the dispersion of absorption coefficient. The optical data are explained in terms of the different oxidation states adopted by the chromium ions into the glass network. It is found that the oxidation state of the chromium depends on its concentration. Across a wide spectral range, 0.2-1.6μm, analysis of the fundamental absorption edge provides values for the average energy band gaps for allowed direct and indirect transitions. The optical absorption coefficient just below the absorption edge varies exponentially with photon energy indicating the presence of Urbach's tail. Such tail is decreased with the increase of the chromium dopant. From the analysis of the optical absorption data, the absorption peak at ground state exciton energy, the absorption at band gap, and the free exciton binding energy are determined. The extinction coefficient data are used to determine the Fermi energy level of the studied glasses. The metallization criterion is obtained and discussed exploring the nature of the glasses. The measured IR spectra of the different glasses are used to throw some light on the optical properties of the present glasses correlating them with their structure and composition.

Study of Cr(VI) adsorption onto magnetite nanoparticles using synchrotron-based X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Yen-Hua; Liu, Dian-Yu; Lee, Jyh-Fu

2018-04-01

In this study, the efficiency of Cr(VI) adsorption onto nano-magnetite was examined by batch experiments, and the Cr(VI) adsorption mechanism was investigated using synchrotron-based X-ray absorption spectroscopy. Magnetite nanoparticles with a mean diameter of 10 nm were synthesized using an inexpensive and simple co-precipitation method. It shows a saturation magnetization of 54.3 emu/g, which can be recovered with an external magnetic field. The adsorption data fitted the Langmuir adsorption isotherm well, implying a monolayer adsorption behavior of Cr(VI) onto nano-magnetite. X-ray absorption spectroscopy results indicate that the adsorption mechanism involves electron transfer between Fe(II) in nano-magnetite (Fe2+OFe3+ 2O3) and Cr(VI) to transform into Cr(III), which may exist as an Fe(III)-Cr(III) mixed solid phase. Moreover, the Cr(III)/Cr(VI) ratio in the final products can be determined by the characteristic pre-edge peak area of Cr(VI) in the Cr K-edge spectrum. These findings suggest that nano-magnetite is effective for Cr(VI) removal from wastewater because it can transform highly poisonous Cr(VI) species into nontoxic Cr(III) compounds, which are highly insoluble and immobile under environmental conditions.

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.

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.

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.

Directionally Aligned Amorphous Polymer Chains via Electrohydrodynamic-Jet Printing: Analysis of Morphology and Polymer Field-Effect Transistor Characteristics.

PubMed

Kim, Yebyeol; Bae, Jaehyun; Song, Hyun Woo; An, Tae Kyu; Kim, Se Hyun; Kim, Yun-Hi; Park, Chan Eon

2017-11-15

Electrohydrodynamic-jet (EHD-jet) printing provides an opportunity to directly assembled amorphous polymer chains in the printed pattern. Herein, an EHD-jet printed amorphous polymer was employed as the active layer for fabrication of organic field-effect transistors (OFETs). Under optimized conditions, the field-effect mobility (μ FET ) of the EHD-jet printed OFETs was 5 times higher than the highest μ FET observed in the spin-coated OFETs, and this improvement was achieved without the use of complex surface templating or additional pre- or post-deposition processing. As the chain alignment can be affected by the surface energy of the dielectric layer in EHD-jet printed OFETs, dielectric layers with varying wettability were examined. Near-edge X-ray absorption fine structure measurements were performed to compare the amorphous chain alignment in OFET active layers prepared by EHD-jet printing and spin coating.

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.

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

Structure of the manganese complex in photosystem II: insights from X-ray spectroscopy.

PubMed Central

Yachandra, Vittal K

2002-01-01

We have used Mn K-edge absorption and Kbeta emission spectroscopy to determine the oxidation states of the Mn complex in the various S states. We have started exploring the new technique of resonant inelastic X-ray scattering spectroscopy; this technique can be characterized as a Raman process that uses K-edge energies (1s to 4p, ca. 6550 eV) to obtain L-edge-like spectra (2p to 3d, ca. 650 eV). The relevance of these data to the oxidation states and structure of the Mn complex is presented. We have obtained extended X-ray absorption fine structure data from the S(0) and S(3) states and observed heterogeneity in the Mn-Mn distances leading us to conclude that there may be three rather than two di-mu-oxo-bridged units present per tetranuclear Mn cluster. In addition, we have obtained data using Ca and Sr X-ray spectroscopy that provide evidence for a heteronuclear Mn-Ca cluster. The possibility of three di-mu-oxo-bridged Mn-Mn moieties and the proximity of Ca is incorporated into developing structural models for the Mn cluster. The involvement of bridging and terminal O ligands of Mn in the mechanism of oxygen evolution is discussed in the context of our X-ray spectroscopy results. PMID:12437873

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

PubMed Central

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

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono-μ-oxo compounds in equivalent oxidation states. The energy shifts observed due to oxidation are also similar for the two different compounds. The study of the different behavior of the XANES pre-edge and main-edge features in conjunction with Kβ XES provides significant information about the oxidation state and character of the ligand environment of manganese atoms. PMID:11459481

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.

X-ray magnetic circular dichroism measured at the Fe K-edge with a reduced intrinsic broadening: x-ray absorption spectroscopy versus resonant inelastic x-ray scattering measurements

NASA Astrophysics Data System (ADS)

Juhin, Amélie; Sainctavit, Philippe; Ollefs, Katharina; Sikora, Marcin; Filipponi, Adriano; Glatzel, Pieter; Wilhelm, Fabrice; Rogalev, Andrei

2016-12-01

X-ray magnetic circular dichroism is measured at the Fe K pre-edge in yttrium iron garnet using two different procedures that allow reducing the intrinsic broadening due to the 1s corehole lifetime. First, deconvolution of XMCD data measured in total fluorescence yield (TFY) with an extremely high signal-to-noise ratio enables a factor of 2.4 to be gained in the XMCD intensity. Ligand field multiplet calculations performed with different values of intrinsic broadening show that deconvolving such high quality XMCD data is similar to reducing the lifetime broadening from a 1s corehole to a 2p corehole. Second, MCD is measured by resonant inelastic x-ray scattering spectroscopy as a function of incident energy and emission energy. Selection of a fixed emission energy, instead of using the TFY, allows enhancing the MCD intensity up to a factor of  ˜4.7. However, this significantly changes the spectral shape of the XMCD signal, which cannot be interpreted any more as an absorption spectrum.

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%.

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.

X-ray absorption spectral studies of copper (II) mixed ligand complexes

NASA Astrophysics Data System (ADS)

Soni, B.; Dar, Davood Ah; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2014-09-01

X-ray absorption spectra at the K-edge of copper have been studied in two copper mixed ligand complexes, one having tetramethyethylenediamine (tmen) and the other having tetraethyethylenediamine (teen) as one of the ligands. The spectra have been recorded at BL-8 dispersive extended X-ray absorption fine structure (EXAFS) beamline at the 2.5 GeV INDUS- 2 synchrotron, RRCAT, Indore, India. The data obtained has been processed using the data analysis program Athena. The energy of the K-absorption edge, chemical shift, edge-width and shift of the principal absorption maximum in the complexes have been determined and discussed. The values of these parameters have been found to be approximately the same in both the complexes indicating that the two complexes possess similar chemical environment around the copper metal atom. The chemical shift has been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length because of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase- uncorrected bond length. Bond length has also been determined by Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The results obtained from LSS and the Fourier transformation methods are comparable with each other, since both are phase uncorrected bond lengths.

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.

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.

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.

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.

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.

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.

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.

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.

Soft X-ray characterization technique for Li batteries under operating conditions.

PubMed

Petersburg, Cole F; Daniel, Robert C; Jaye, Cherno; Fischer, Daniel A; Alamgir, Faisal M

2009-09-01

O K-edge and Co L-edge near-edge X-ray absorption fine structure has been used to examine the cathode of an intact solid-state lithium ion battery. The novel technique allowed for the simultaneous acquisition of partial electron yield and fluorescence yield data during the first charge cycle of a LiCoO(2)-based battery below the intercalation voltage. The chemical environments of oxygen and cobalt at the surface are shown to differ chemically from those in the bulk. The present design enables a wide variety of in situ spectroscopies, microscopies and scattering techniques.

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

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.

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

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

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.

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

PubMed

Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

2018-03-01

The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

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

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

Formation of nanostructures in Eu3+ doped glass-ceramics: an XAS study.

PubMed

Pellicer-Porres, J; Segura, A; Martínez-Criado, G; Rodríguez-Mendoza, U R; Lavín, V

2013-01-16

We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu(3+) doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-L(III) edges. The Eu environment in the glass samples is observed to be similar to that of EuF(3). Complementary x-ray diffraction experiments show that thermal annealing creates β-PbF(2) type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-L(III) edge shows that after the thermal treatment most lead atoms form a PbO amorphous phase and that only 10% of the lead atoms remain available to form β-PbF(2) type nanocrystals. Both x-ray diffraction and absorption point to a high Eu content in the nanocrystals. Our study suggests new approaches to the oxyfluoride glass-ceramic synthesis in order to further improve their properties.

Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

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

Lahariya, Vikas

The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

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.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, 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 CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (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). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

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

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.

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

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

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.

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 is a multi-program national laboratory operated for DOE by Battelle under Contract # AC05-76RL01830.« less

X-ray absorption spectroscopy and neutron diffraction study of the perovskite-type rare-earth cobaltites

NASA Astrophysics Data System (ADS)

Sikolenko, V.; Efimova, E.; Franz, A.; Ritter, C.; Troyanchuk, I. O.; Karpinsky, D.; Zubavichus, Y.; Veligzhanin, A.; Tiutiunnikov, S. I.; Sazonov, A.; Efimov, V.

2018-05-01

Correlations between local and long-range structure distortions in the perovskite-type RE1-xSrxCoO3-δ (RE = La, Pr, Nd; x = 0.0 and 0.5) compounds have been studied at room temperature by extended X-ray absorption fine structure (EXAFS) at the Co K-edge and high-resolution neutron powder diffraction (NPD). The use of two complementary experimental techniques allowed us to explore the influence of the type of rare-earth element and strontium substitution on unusual behavior of static and dynamic features of both the Co-O bond lengths.

Behaviour of niobium during early Earth’s differentiation: insights from its local structure and oxidation state in silicate melts at high pressure

NASA Astrophysics Data System (ADS)

Sanloup, C.; Cochain, B.; de Grouchy, C.; Glazyrin, K.; Konôpkova, Z.; Liermann, H.-P.; Kantor, I.; Torchio, R.; Mathon, O.; Irifune, T.

2018-02-01

Niobium (Nb) is one of the key trace elements used to understand Earth’s formation and differentiation, and is remarkable for its deficiency relative to tantalum in terrestrial rocks compared to the building chondritic blocks. In this context, the local environment of Nb in silica-rich melts and glasses is studied by in situ x-ray absorption spectroscopy (XAS) at high pressure (P) up to 9.3 GPa and 1350 K using resistive-heating diamond-anvil cells. Nb is slightly less oxidized in the melt (intermediate valence between  +4 and  +5) than in the glass (+5), an effect evidenced from the shift of the Nb-edge towards lower energies. Changes in the pre-edge features are also observed between melt and glass states, consistently with the observed changes in oxidation state although likely enhanced by temperature (T) effects. The oxidation state of Nb is not affected by pressure neither in the molten nor glassy states, and remains constant in the investigated P-range. The Nb-O coordination number is constant and equal to 6.3+/-0.4 below 5 GPa, and only progressively increases up to 7.1+/-0.4 at 9.3 GPa, the maximum P investigated. If these findings were to similarly apply to basaltic melts, that would rule out the hypothesis of Nb/Ta fractionation during early silicate Earth’s differentiation, thus reinforcing the alternative hypothesis of fractionation during core formation on reduced pre-planetary bodies.

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

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

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

DOE PAGES

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

2016-02-15

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character

DOE PAGES

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.; ...

2017-09-18

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and here we probe this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L 2,3- edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-drivenmore » alcohol oxidation reactions, with similar findings. On the whole, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co- catalyst system.« less

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.

Ferromagnetism regulated by edged cutting and optical identification in monolayer PtSe2 nanoribbons

NASA Astrophysics Data System (ADS)

Meng, Ming; Zhang, QiZhen; Wang, Lifen; Shan, Yun; Du, Yuandong; Qin, Nan; Liu, Lizhe

2018-06-01

Regulation of ferromagnetism and electronic structure in PtSe2 nanostructures has attracted much attention because of its potential in spintronics. The magnetic and optical properties of PtSe2 nanoribbons with different edge reconstruction and external deformations are calculated by density function theory. In 1 T phase PtSe2 nanoribbons, the ferromagnetism induced by spin polarization of exposed Pt or Se atoms is decreased with the reducing nanoribbon width. For smaller nanoribbon, the magnetism can be regulated by external strain more easily. However, the magnetism cannot occur in 1 H phase PtSe2 nanoribbon. The absorption spectra are suggested to identify the nanoribbon structural changes in detail. Our results suggest the use of edge reconstruction and strain engineering in spintronics applications.

The BALDER Beamline at the MAX IV Laboratory

NASA Astrophysics Data System (ADS)

Klementiev, K.; Norén, K.; Carlson, S.; Sigfridsson Clauss, K. G. V.; Persson, I.

2016-05-01

X-ray absorption spectroscopy (XAS) includes well-established methods to study the local structure around the absorbing element - extended X-ray absorption fine structure (EXAFS), and the effective oxidation number or to quantitatively determine the speciation of an element in a complex matrix - X-ray absorption near-edge structure (XANES). The increased brilliance and intensities available at the new generation of synchrotron light sources makes it possible to study, in-situ and in-operando, much more dilute systems with relevance for natural systems, as well as the micro-scale variability and dynamics of chemical reactions on the millisecond time-scale. The design of the BALDER beamline at the MAX IV Laboratory 3 GeV ring has focused on a high flux of photons in a wide energy range, 2.4-40 keV, where the K-edge is covered for the elements S to La, and the L 3-edge for all elements heavier than Sb. The overall design of the beamline will allow large flexibility in energy range, beam size and data collection time. The other focus of the beamline design is the possibility to perform multi-technique analyses on samples. Development of sample environment requires focus on implementation of auxiliary methods in such a way that techniques like Fourier transform infrared (FTIR) spectroscopy, UV-Raman spectroscopy, X-ray diffraction and/or mass spectrometry can be performed simultaneously as the XAS study. It will be a flexible system where different instruments can be plugged in and out depending on the needs for the particular investigation. Many research areas will benefit from the properties of the wiggler based light source and the capabilities to perform in-situ and in-operando measurements, for example environmental and geochemical sciences, nuclear chemistry, catalysis, materials sciences, and cultural heritage.

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.

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.

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.

Wave Function Engineering in CdSe/PbS Core/Shell Quantum Dots.

PubMed

Wieliczka, Brian M; Kaledin, Alexey L; Buhro, William E; Loomis, Richard A

2018-05-25

The synthesis of epitaxial CdSe/PbS core/shell quantum dots (QDs) is reported. The PbS shell grows in a rock salt structure on the zinc blende CdSe core, thereby creating a crystal structure mismatch through additive growth. Absorption and photoluminescence (PL) band edge features shift to lower energies with increasing shell thickness, but remain above the CdSe bulk band gap. Nevertheless, the profiles of the absorption spectra vary with shell growth, indicating that the overlap of the electron and hole wave functions is changing significantly. This leads to over an order of magnitude reduction of absorption near the band gap and a large, tunable energy shift, of up to 550 meV, between the onset of strong absorption and the band edge PL. While the bulk valence and conduction bands adopt an inverse type-I alignment, the observed spectroscopic behavior is consistent with a transition between quasi-type-I and quasi-type-II behavior depending on shell thickness. Three effective mass approximation models support this hypothesis and suggest that the large difference in effective masses between the core and shell results in hole localization in the CdSe core and a delocalization of the electron across the entire QD. These results show the tuning of wave functions and transition energies in CdSe/PbS nanoheterostructures with prospects for use in optoelectronic devices for luminescent solar concentration or multiexciton generation.

Pulsed UV laser-induced modifications in optical and structural characteristics of alpha-irradiated PM-355 SSNTD.

PubMed

Alghamdi, S S; Farooq, W A; Baig, M R; Algarawi, M S; Alrashidi, Talal Mohammed; Ali, Syed Mansoor; Alfaramawi, K

2017-10-01

Pre- and postalpha-exposed PM-355 detectors were irradiated using UV laser with different number of pulses (100, 150, 200, 300, and 400). UV laser beam energy of 20mJ per pulse with a pulse width of 9ns was incident on an area of 19.6mm 2 of the samples. XRD spectra indicated that for both reference and UV-irradiated samples, the structure is amorphous, but the crystallite size increases upon UV irradiation. The same results were obtained from SEM analysis. Optical properties of PM-355 polymeric solid-state nuclear track detectors were also investigated. Absorbance measurements for all PM-355 samples in the range of 200-400nm showed that the absorption edge had a blue shift up to a certain value, and then, it had an oscillating behavior. Photoluminescence spectra of PM-355 at 250nm revealed a decrease in the broadband peak intensity as a function of the number of UV pulses, while the wavelengths corresponding to the peaks had random shifts. Copyright © 2017 Elsevier Ltd. All rights reserved.

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

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.

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

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

A new heterometallic hybrid based on polymeric iodoplumbate and lanthanide metal-carboxylic coordination polycation

NASA Astrophysics Data System (ADS)

Gong, An-Weng; Wu, Hong-Yan; Lian, Zhao-Xun; Dong, Hai-Jun; Li, Hao-Hong; Chen, Zhi-Rong

2013-03-01

A 3-D supramolecular hybrid {[La(EPC)3(H2O)3]2(Pb6I18)}n (EPC+ = N-ethyl-pyridium-4-carboxylate) (1) has been structurally determined, which assume significance for its incorporating lanthanide metal-carboxylic coordination polycation into polymeric iodoplumbate to get heterometallics. 1 consists of 1-D (PbI)n6n- zigzag-like anion chains with lanthanide metalcarboxylic [La(EPC)3(HO)3]n3n+ polycations, which arrange in a criss-cross configuration. C-H⋯I and C-H⋯O hydrogen bonds among inorganic anions and polycations contribute to the formation of a 3-D supramolecular framework. Moreover, the framework displays an absorption edge at 2.46 eV which is comparable to PbI2's absorption edge.

QUANTIFYING HAZARDOUS SPECIES IN PARTICULATE MATTER DERIVED FROM FOSSIL-FUEL COMBUSTION

EPA Science Inventory

An analysis protocol that combines X-ray absorption near-edge structure spectroscopy with selective leaching has been developed to examine hazardous species in size- segregated particulate matter (PM) samples derived from the combustion of fossil fuels. The protocol has been used...

Legacy phosphorus in calcareous soils: Effects of long-term poultry litter application

USDA-ARS?s Scientific Manuscript database

The effect of manure application on soil phosphorus has been intensively studied with modifications of the Hedley sequential fractionation procedure, X ray absorption near edge structure spectroscopy, and 31P nuclear magnetic resonance. Modern sequential fractionation techniques, coupled with phosph...

Effects of rare-earth size on the electronic structure of La1−xLuxVO3.

PubMed

Chen, B; Laverock, J; Newby, D; McNulty, J F; Smith, K E; Glans, P-A; Guo, J-H; Qiao, R-M; Yang, W-L; Lees, M R; Tung, L D; Singh, R P; Balakrishnan, G

2015-03-18

The electronic structure of La(1-x)Lu(x)VO(3)(x = 0, 0.2, 0.6 and 1) single crystals has been investigated using soft x-ray absorption spectroscopy, soft x-ray emission spectroscopy, and resonant soft x-ray inelastic scattering to study the effects of rare-earth size. The x-ray absorption and emission spectra at the O K-edge present a progressive evolution with R-site cation, in agreement with local spin density approximation calculations. This evolution with R, together with the temperature dependence of the O K-edge spectra, is attributed to changes in the crystal structure of La(1-x)Lu(x)VO(3). The crystal-field dd. excitations probed by resonant inelastic x-ray scattering at the V L(3)-edge exhibit an increase in energy and enhanced intensity with the decrease of R-site ionic radius, which is mainly attributed to the increased tilting magnitude of the VO(6) octahedra. Upon cooling to ~95 K, the dd* excitations are prominently enhanced in relative Intensity, in agreement with the formation of the Jahn.Teller distortion int he orbital ordering phase. Additionally, the dd* transitions of the mixed compounds are noticeably suppressed with respect to those of the pure compounds, possibly owing to the formation of C-type orbital ordering induced by large R-site size variances.

Core x-ray spectra in semiconductors and the Mahan-Nozieres-De Dominicis model

NASA Astrophysics Data System (ADS)

Livins, Peteris

1998-10-01

The Mahan-Nozières-De Dominicis (MND) model of core x-ray spectra is examined for semiconductors. Due to the finite band gap, the Anderson orthogonality does not occur, and thus spectra near the band edge can be calculated without the shakeup contribution. For semiconductors, and not only for metals, we investigate whether the remaining many-particle dynamic exchange effect of the MND model, or so-called replacement, can significantly alter x-ray spectral shapes near the band edge from those obtained from a straightforward final-state rule. For both emission and absorption, in the absence of shakeup, an exact formulation suitable for materials with band structure is discussed. A numerical model for a semiconductor with a 1-eV band gap demonstrates the band-edge modifications, and shows a 50% effect at the band edge, indicating that this dynamic exchange effect can be significant and should be considered in any specific emission or absorption calculation for a semiconductor. Although the ineffectiveness of the orthogonality theorem in semiconductors is emphasized, a suppression near the band edge also remains a possibility. Included is a discussion on the breakdown of the final-state rule. In addition, connection is made to the determinantal approach of Ohtaka and Tanabe.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

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

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

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

Smith, Euan; Kempson, Ivan; Juhasz, Albert L.

The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations ofmore » {mu}XRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant.« less

TXM-Wizard: a program for advanced data collection and evaluation in full-field transmission X-ray microscopy

PubMed Central

Liu, Yijin; Meirer, Florian; Williams, Phillip A.; Wang, Junyue; Andrews, Joy C.; Pianetta, Piero

2012-01-01

Transmission X-ray microscopy (TXM) has been well recognized as a powerful tool for non-destructive investigation of the three-dimensional inner structure of a sample with spatial resolution down to a few tens of nanometers, especially when combined with synchrotron radiation sources. Recent developments of this technique have presented a need for new tools for both system control and data analysis. Here a software package developed in MATLAB for script command generation and analysis of TXM data is presented. The first toolkit, the script generator, allows automating complex experimental tasks which involve up to several thousand motor movements. The second package was designed to accomplish computationally intense tasks such as data processing of mosaic and mosaic tomography datasets; dual-energy contrast imaging, where data are recorded above and below a specific X-ray absorption edge; and TXM X-ray absorption near-edge structure imaging datasets. Furthermore, analytical and iterative tomography reconstruction algorithms were implemented. The compiled software package is freely available. PMID:22338691

Valence holes observed in nanodiamonds dispersed in water

NASA Astrophysics Data System (ADS)

Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F.

2015-02-01

Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed.Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed. Electronic supplementary information (ESI) available: Experimental methods, details on XAS/XES normalization and background correction procedures. See DOI: 10.1039/c4nr06639a

Effects of X-ray irradiation on the Eu3+ → Eu2+ conversion in CaAl2O4 phosphors

NASA Astrophysics Data System (ADS)

Gomes, Manassés A.; Carvalho, Jéssica C.; Andrade, Adriano B.; Rezende, Marcos V.; Macedo, Zélia S.; Valerio, Mário E. G.

2018-01-01

This paper reports structural and luminescence properties of Eu-doped CaAl2O4 produced by an alternative sol-gel method using coconut water. Results of differential thermal analysis (DTA), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) allowed us to identify the best synthesis conditions for sample preparation. Simultaneous measurements of X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) were also performed in the X-ray energy range of the Eu LIII edge. Results from photoluminescence (PL) showed only the characteristic Eu3+ emission. However, radioluminescence emission spectra from Eu-doped CaAl2O4 shows a process of conversion of Eu3+ to Eu2+, which is induced by X-ray irradiation and is dependent on the radiation dose energy. X-ray absorption near edge structure (XANES) measurements corroborate Eu reduction due to irradiation, showing that only the Eu3+ ion is present in stable form in the CaAl2O4.

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.

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

The influence of reaction times on structural, optical and luminescence properties of cadmium telluride nanoparticles prepared by wet-chemical process

NASA Astrophysics Data System (ADS)

Kiprotich, Sharon; Dejene, Francis B.; Ungula, Jatani; Onani, Martin O.

2016-01-01

This paper explains one pot synthesis of type II water soluble L-cysteine capped cadmium telluride (CdTe) core shell quantum dots using cadmium acetate, potassium tellurite and L-cysteine as the starting materials. The reaction was carried out in a single three necked flask without nitrogen under reflux at 100 °C. Results from PL show a sharp absorption excitonic band edge of the CdTe core with respect to the core shell which loses its shoulder during the growth of the shell on the core. The PL spectra indicate a drastic shift in emission window of the core which is simultaneously accompanied by an increase in emission intensity. X-ray diffraction pattern confirms the formation of hexagonal phase for all samples. Some difference in absorption edges were observed due to varying synthesis time of CdTe NPs. The position of the absorption band is observed to shift towards the lower wavelength side for shorter durations of synthesis.

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

NASA Astrophysics Data System (ADS)

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

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

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

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.

Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt LIII XAFS Studies

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

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

2008-02-28

The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied (Al2O3, BaO/Al2O3, Pt/Al2O3 and Pt-BaO/Al2O3) were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas phase oxygen. In the platinum-containing samples, the presence of Pt-O species plays an important role in the formation of sulfate species. Even if bariummore » and aluminum sites are available for SO2 to form sulfate, for the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, S XANES spectroscopy results show that barium sulfates are preferentially produced over aluminum sulfates . When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the redox nature of the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g. SO2+H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g. SO2+O2) continue to show the presence of Pt-O bonds. In addition, the former condition was found to give rise to a higher degree of Pt sintering than the latter one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g. sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.« less

Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt Llll XAFS Studies

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

Kim,D.; Kwak, J.; Szanyi, J.

2008-01-01

The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied [Al2O3, BaO(x; x = 8 or 20 wt %)/Al2O3, Pt(2.5 wt %)/Al2O3, and Pt(2 wt %)-BaO(x; x = 8 or 20 wt %)/Al2O3] were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas-phase oxygen. In the platinum-containing samples, themore » presence of Pt-O species plays an important role in the formation of sulfate species. For the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, both baria and alumina phases are available for sulfation. S XANES results show that barium sulfates are formed preferentially over aluminum sulfates. When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g., SO2/H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g., SO2/O2) continue to show the presence of Pt-O bonds. In addition, a reducing environment was found to cause Pt sintering in greater extent than an oxidizing one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g., sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.« less

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.

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

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

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

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

2014-10-14

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

Sol-gel synthesis and optical properties of titanium dioxide thin film

NASA Astrophysics Data System (ADS)

Ullah, Irfan; Khattak, Shaukat Ali; Ahmad, Tanveer; Saman; Ludhi, Nayab Ali

2018-03-01

The titanium dioxide (TiO2) is synthesized by sol-gel method using titanium-tetra-iso-propoxide (TTIP) as a starting material, and deposited on the pre-cleaned glass substrate using spin coating technique at optimized parameters. Energy dispersive X-ray (EDX) spectroscopy confirms successful TiO2 growth. The optical properties concerning the transmission and absorption spectra show 85% transparency and 3.28 eV wide optical band gap for indirect transition, calculated from absorbance. The exponential behavior of absorption edge is observed and attributed to the localized states electronic transitions, curtailed in the indirect band gap of the thin film. The film reveals decreasing refractive index with increasing wavelength. The photoluminescence (PL) study ascertains that luminescent properties are due to the surface defects.

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.

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.

Unoccupied states in Cu and Zn octaethyl-porphyrin and phthalocyanine.

PubMed

Cook, Peter L; Yang, Wanli; Liu, Xiaosong; García-Lastra, Juan María; Rubio, Angel; Himpsel, F J

2011-05-28

Copper and zinc phthalocyanines and porphyrins are used in organic light emitting diodes and dye-sensitized solar cells. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Cu 2p and Zn 2p edges, the unoccupied valence states at the Cu and Zn atoms are probed and decomposed into 3d and 4s contributions with the help of density functional calculations. A comparison with the N 1s edge provides the 2p states of the N atoms surrounding the metal, and a comparison with inverse photoemission provides a combined density of states. © 2011 American Institute of Physics

Operando Analyses of Solar Fuels Light Absorbers and Catalysts

DOE PAGES

Lewerenz, Hans -Joachim; Lichterman, Michael F.; Richter, Matthias H.; ...

2016-06-06

Operando synchrotron radiation photoelectron spectroscopy in the tender X-ray energy range has been used to obtain information on the energy-band relations of semiconductor and metal-covered semiconductor surfaces while in direct contact with aqueous electrolytes under potentiostatic control. The system that was investigated consists of highly doped Si substrates that were conformally coated with ~70 nm titania films produced by atomic-layer deposition. TiO 2/electrolyte and Si/TiO 2 /Ni/electrolyte interfaces were then analyzed by synchrotron radiation photoelectron spectroscopy. The PES data allows for determination of the flat-band position and identification of potential regions in which Fermi level pinning, depletion, or accumulation occurred. Operandomore » X-ray absorption spectroscopy (XAS) techniques were additionally used to investigate the properties of heterogeneous electrocatalysts for the oxygen-evolution reaction. Operando XAS including the pre-edge, edge and EXAFS regions allowed the development of a detailed picture of the catalysts under operating conditions, and elucidated the changes in the physical and electronic structure of the catalyst that accompanied increases in the applied potential. Specifically, XAS data, combined with DFT studies, indicated that the activity of the electrocatalyst correlated with the formation of Fe dopant sites in γ-NiOOH.« less

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.

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.

Molecular species forming at the α-Fe2O3 nanoparticle-aqueous solution interface.

PubMed

Ali, Hebatallah; Seidel, Robert; Pohl, Marvin N; Winter, Bernd

2018-05-21

We report on electronic structure measurements of the interface between hematite nanoparticles (6 nm diameter) and aqueous solutions. Using soft X-ray photoelectron spectroscopy from a liquid microjet we detect valence and core-level photoelectrons as well as Auger electrons from liquid water, from the nanoparticle-water interface, and from the interior of the aqueous-phase nanoparticles. Most noteworthy, the method is shown to be sufficiently sensitive for the detection of adsorbed hydroxyl species, resulting from H 2 O dissociation at the nanoparticle surface in aqueous solution. We obtain signal from surface OH from resonant, non-resonant, and from so-called partial-electron-yield X-ray absorption (PEY-XA) spectra. In addition, we report resonant photoelectron measurements at the iron 2p excitation. The respective Fe iron 2p 3/2 edge (L 3 -edge) PEY-XA spectra exhibit two main absorption peaks with their energies being sensitive to the chemical environment of the Fe 3+ ions at the nanoparticle-solution interface. This manifests in the 10 D q value which is a measure of the ligand-field strength. Furthermore, an observed intensity variation of the pre-peak, when comparing the PEY-XA spectra for different iron Auger-decay channels, can be assigned to different extents of electron delocalization. From the experimental fraction of local versus non-local autoionization signals we then find a very fast, approximately 1 fs, charge transfer time from interfacial Fe 3+ into the environment. The present study, which is complementary to ambient-pressure photoemission studies on solid-electrolyte systems, also highlights the multiple aspects of photoemission that need to be explored for a full characterization of the transition-metal-oxide nanoparticle surface in aqueous phase.

Structural analysis of strontium in human teeth treated with surface pre-reacted glass-ionomer filler eluate by using extended X-ray absorption fine structure analysis.

PubMed

Uo, Motohiro; Wada, Takahiro; Asakura, Kiyotaka

2017-03-31

The bioactive effects of strontium released from surface pre-reacted glass-ionomer (S-PRG) fillers may aid in caries prevention. In this study, the local structure of strontium taken up by teeth was estimated by extended X-ray absorption fine structure analysis. Immersing teeth into S-PRG filler eluate increased the strontium content in enamel and dentin by more than 100 times. The local structure of strontium in enamel and dentin stored in distilled water was the same as that in synthetic strontium-containing hydroxyapatite (SrHAP). Moreover, the local structure of strontium in enamel and dentin after immersion in the S-PRG filler eluate was also similar to that of SrHAP. After immersion in the S-PRG filler eluate, strontium was suggested to be incorporated into the hydroxyapatite (HAP) of enamel and dentin at the calcium site in HAP.

Atomistic simulation and XAS investigation of Mn induced defects in Bi{sub 12}TiO{sub 20}

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

Rezende, Marcos V dos S.; Santos, Denise J.; Jackson, Robert A.

2016-06-15

This work reports an investigation of the valence and site occupancy of Mn dopants in Bi{sub 12}TiO{sub 20} (BTO: Mn) host using X-ray Absorption (XAS) and atomistic simulation techniques based on energy minimisation. X-ray Absorption Near Edge Structure (XANES) at the Mn K-edges gave typical results for Mn ions with mixed valences of 3+ and 4+. Extended X-ray Absorption Fine Structure (EXAFS) results indicated that Mn ions are probably substituted at Ti sites. Atomistic simulation was performed assuming the incorporation of Mn{sup 2+}, Mn{sup 3+} and Mn{sup 4+} ions at either Bi{sup 3+} or Ti{sup 4+} sites, and the resultsmore » were compared to XANES and EXAFS measurements. Electrical conductivity for pure and doped samples was used to evaluate the consistency of the proposed model. - Graphical abstract: The structure of Bi{sub 12}TiO{sub 20} (BTO). Display Omitted - Highlights: • Pure and Mn-doped Bi{sub 12}TiO{sub 20} samples were studied by experimental techniques combined with atomistic simulation. • Good agreement between experimental and simulation results was obtained. • XANES results suggest a mixture of 3+ and 4+ valences for Mn, occupying the Ti4+ site in both cases. • Charge compensation by holes is most energetically favoured, explaining the enhancement observed in AC dark conductivity.« less

Formation of graded vanadium oxide (V-O compound) under strong gravitational field

NASA Astrophysics Data System (ADS)

Khandaker, Jahirul Islam; Tokuda, Makoto; Ogata, Yudai; Januszko, Kamila; Nishiyama, Tadao; Yoshiasa, Akira; Mashimo, Tsutomu

2015-05-01

Sedimentation of atoms induced under strong gravitational field gives a tool for controlling elemental compositions in condensed matter. We performed a strong-gravity experiment (0.397 × 106 G at 400 °C for 24 h) on a V2O5 polycrystal using the high-temperature ultracentrifuge to examine the composition change and further the structure change. The graded composition structure of V and O was formed along gravity direction, where V increases and O decreases with gravity. It was found by the x-ray diffraction and Raman scattering method that VO2 and V2O3 phases appeared and the amounts increased, while one of the V2O5 phase decreased gradually along gravity direction. The X-ray absorption near edge structure spectra analysis identified the chemical valency decrease (+5 to +3). The UV-Vis absorption spectroscopy addressed the shifting in center of major absorption peak to longer wavelength (red shift) with the increase in gravitational field. The tail absorption peak (band gap 2.09 eV) at strong gravity region in the graded structure showed transparent conductive oxide.

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

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.

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.

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.

Oxidation and crystal field effects in uranium

NASA Astrophysics Data System (ADS)

Tobin, J. G.; Yu, S.-W.; Booth, C. H.; Tyliszczak, T.; Shuh, D. K.; van der Laan, G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Bagus, P. S.

2015-07-01

An extensive investigation of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (U O2) , uranium trioxide (U O3) , and uranium tetrafluoride (U F4) . A discussion of the role of nonspherical perturbations, i.e., crystal or ligand field effects, will be presented.

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

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and here we probe this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L 2,3- edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-drivenmore » alcohol oxidation reactions, with similar findings. On the whole, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co- catalyst system.« less

Thermal effects on the structural properties of tungsten oxide nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Tsung-Yeh; Wu, Chung-Yi; Tsai, Meng-Hung; Lin, Hong-Ming; Tsai, Wen-Li; Hwu, Yeukuang

2004-06-01

Tungsten oxide nanoparticles are prepared by evaporating and oxidizing the tungsten boat in helium and oxygen atmosphere and then quenched to the liquid nitrogen temperature. The as-prepared tungsten oxide nanoparticles are porous-free with uniform size. The morphology and particle size distribution of the as-prepared and after sinter treatments tungsten oxide nanoparticles are revealed by TEM and AFM. The long-range order of these nanoparticles can be examined by X-ray diffraction technique. The as-prepared nanoparticles exhibit a mixture structure of monoclinic and hexagonal crystals. Preliminary X-ray diffraction results indicate that the hexagonal structure is transformed to monoclinic structure after annealing to above 600°C. In order to better distinguish the structural properties of the tungsten oxide (WO3- x) nanoparticles before and after annealing, the X-ray absorption spectrum technique is utilized; thus, the detailed local atomic arrangement of oxygen and/or tungsten can be determined. According to the XAS result, the shape of the W L3-edge undergoes no considerable changes. This infers that structural transformation of tungsten oxide nanoparticle may be caused by the migration of oxygen after sintering. From the O K-edge of absorption spectrum, it suggests that a mixture phase structure is obtained when sintered below 300°C. And this result indicates that heat treatment to approximately 600°C produces a stable structure of a monoclinic crystal of WO3.

Reflectivity Around the Gold M-Edges of X-ray Reflector of the Soft X-Ray Telescope Onboard ASTRO-H

NASA Technical Reports Server (NTRS)

Kurashimaa, Sho; Furuzawa, Akihiro; Sato, Toshiki; Kikuchia, Naomichi; Nakaniwaa, Nozomi; Maeda, Yoshitomo; Ishida, Manabu; Izuka, Ryo; Okajima, Takashi; Mori, Hideyuki;

Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal-Ligand Intersystem Crossing Transients.

PubMed

Guda, Sergey A; Guda, Alexander A; Soldatov, Mikhail A; Lomachenko, Kirill A; Bugaev, Aram L; Lamberti, Carlo; Gawelda, Wojciech; Bressler, Christian; Smolentsev, Grigory; Soldatov, Alexander V; Joly, Yves

2015-09-08

Accurate modeling of the X-ray absorption near-edge spectra (XANES) is required to unravel the local structure of metal sites in complex systems and their structural changes upon chemical or light stimuli. Two relevant examples are reported here concerning the following: (i) the effect of molecular adsorption on 3d metals hosted inside metal-organic frameworks and (ii) light induced dynamics of spin crossover in metal-organic complexes. In both cases, the amount of structural models for simulation can reach a hundred, depending on the number of structural parameters. Thus, the choice of an accurate but computationally demanding finite difference method for the ab initio X-ray absorption simulations severely restricts the range of molecular systems that can be analyzed by personal computers. Employing the FDMNES code [Phys. Rev. B, 2001, 63, 125120] we show that this problem can be handled if a proper diagonalization scheme is applied. Due to the use of dedicated solvers for sparse matrices, the calculation time was reduced by more than 1 order of magnitude compared to the standard Gaussian method, while the amount of required RAM was halved. Ni K-edge XANES simulations performed by the accelerated version of the code allowed analyzing the coordination geometry of CO and NO on the Ni active sites in CPO-27-Ni MOF. The Ni-CO configuration was found to be linear, while Ni-NO was bent by almost 90°. Modeling of the Fe K-edge XANES of photoexcited aqueous [Fe(bpy)3](2+) with a 100 ps delay we identified the Fe-N distance elongation and bipyridine rotation upon transition from the initial low-spin to the final high-spin state. Subsequently, the X-ray absorption spectrum for the intermediate triplet state with expected 100 fs lifetime was theoretically predicted.

Rutherford Backscattering Spectrometry studies of 100 keV nitrogen ion implanted polypropylene polymer

NASA Astrophysics Data System (ADS)

Chawla, Mahak; Aggarwal, Sanjeev; Sharma, Annu

2017-09-01

The effect of nitrogen ion implantation on the structure and composition in polypropylene (PP) polymer has been studied. Implantation was carried out using 100 keV N+ ions at different fluences of 1 × 1015, 1 × 1016 and 1 × 1017 ions cm-2 with beam current density of ∼0.65 μA cm-2. Surface morphological changes in the pre- and post-implanted PP specimens have been studied using Rutherford Backscattering Spectrometry (RBS) and UV-Visible Spectroscopy. The spatial distribution of implantation induced modification in the form of carbonization and dehydrogenation in the near surface region of PP matrix, the projected range, retained dose of implanted nitrogen, the various elements present in the implanted layers and their differential cross-sections have been analyzed using RBS spectra. RUMP simulation yielded an increase in the concentration of carbon near the surface from 33 at.% (virgin) to 42 at.% at fluence of 1 × 1017 N+ cm-2. Further, optical absorption has been found to increase with a shift in the absorption edge from UV towards visible region with increasing fluence. UV-Vis absorption spectra also indicate a drastic decrease in optical energy gap from 4.12 eV (virgin) to 0.25 eV (1 × 1017 N+ cm-2) indicating towards the formation of carbonaceous network in the implanted region. All these changes observed using UV-Visible have been further correlated with the outcomes of the RBS characterization.

Insights from soft X-rays: the chlorine and sulfur sub-structures of a CK2alpha/DRB complex.

PubMed

Raaf, Jennifer; Issinger, Olaf-Georg; Niefind, Karsten

2008-09-01

The diffraction pattern of a protein crystal is normally a product of the interference of electromagnetic waves scattered by electrons of the crystalline sample. The diffraction pattern undergoes systematic changes in case additionally X-ray absorption occurs, meaning if the wavelength of the primary X-ray beam is relatively close to the absorption edge of selected elements of the sample. The resulting effects are summarized as "anomalous dispersion" and can be always observed with "soft" X-rays (wavelength around 2 A) since they match the absorption edges of sulfur and chlorine. A particularly useful application of this phenomenon is the experimental detection of the sub-structures of the anomalous scatterers in protein crystals. We demonstrate this here with a crystal of a C-terminally truncated variant of human CK2alpha to which two molecules of the inhibitor 5,6-dichloro-1-beta-D-ribo-furanosyl-benzimidazole (DRB) are bound. The structure of this co-crystal has been solved recently. For this study we measured an additional diffraction data set at a wavelength of 2 A which showed strong anomalous dispersion effects. On the basis of these effects we detected all sulfur atoms of the protein, the two liganded DRB molecules and a total of 16 additional chloride ions some of them emerging at positions filled with water molecules in previous structure determinations. A number of chloride ions are bound to structural and functional important locations fitting to the constitutive activity and the acidophilic substrate specificity of the enzyme.

Iron phosphate glasses: Bulk properties and atomic scale structure

NASA Astrophysics Data System (ADS)

Joseph, Kitheri; Stennett, Martin C.; Hyatt, Neil C.; Asuvathraman, R.; Dube, Charu L.; Gandy, Amy S.; Govindan Kutty, K. V.; Jolley, Kenny; Vasudeva Rao, P. R.; Smith, Roger

2017-10-01

Bulk properties such as glass transition temperature, density and thermal expansion of iron phosphate glass compositions, with replacement of Cs by Ba, are investigated as a surrogate for the transmutation of 137Cs to 137Ba, relevant to the immobilisation of Cs in glass. These studies are required to establish the appropriate incorporation rate of 137Cs in iron phosphate glass. Density and glass transition temperature increases with the addition of BaO indicating the shrinkage and reticulation of the iron phosphate glass network. The average thermal expansion coefficient reduces from 19.8 × 10-6 K-1 to 13.4 × 10-6 K-1, when 25 wt. % of Cs2O was replaced by 25 wt. % of BaO in caesium loaded iron phosphate glass. In addition to the above bulk properties, the role of Ba as a network modifier in the structure of iron phosphate glass is examined using various spectroscopic techniques. The FeII content and average coordination number of iron in the glass network was estimated using Mössbauer spectroscopy. The FeII content in the un-doped iron phosphate glass and barium doped iron phosphate glasses was 20, 21 and 22 ± 1% respectively and the average Fe coordination varied from 5.3 ± 0.2 to 5.7 ± 0.2 with increasing Ba content. The atomic scale structure was further probed by Fe K-edge X-ray absorption spectroscopy. The average coordination number provided by extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure was in good agreement with that given by the Mössbauer data.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

NASA Astrophysics Data System (ADS)

Klysubun, Wantana; Ravel, Bruce; Klysubun, Prapong; Sombunchoo, Panidtha; Deenan, Weeraya

2013-06-01

Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO2; 10 % Na2O; 10 % CaO) bearing lead oxide between 2-16 %. Iron (1.5-9.4 % Fe2O3) and manganese (1.7 % MnO) are present in larger abundance than the other 3 d transition metals detected (0.04-0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L 3-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.

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.

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.

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.

Alteration of human serum albumin tertiary structure induced by glycation. Spectroscopic study

NASA Astrophysics Data System (ADS)

Szkudlarek, A.; Maciążek-Jurczyk, M.; Chudzik, M.; Równicka-Zubik, J.; Sułkowska, A.

2016-01-01

The modification of human serum albumin (HSA) structure by non-enzymatic glycation is one of the underlying factors that contribute to the development of complications of diabetes and neurodegenerative diseases. The aim of the present work was to estimate how glycation of HSA altered its tertiary structure. Changes of albumin conformation were investigated by comparison of glycated (gHSA) and non-glycated human serum albumin (HSA) absorption spectra, red edge excitation shift (REES) and synchronous spectra. Effect of glycation on human serum albumin tertiary structure was also investigated by 1H NMR spectroscopy. Formation of gHSA Advanced Glycation End-products (AGEs) caused absorption of UV-VIS light between 310 nm and 400 nm while for non-glycated HSA in this region no absorbance has been registered. Analysis of red edge excitation shift effect allowed for observation of structural changes of gHSA in the hydrophobic pocket containing the tryptophanyl residue. Moreover changes in the microenvironment of tryptophanyl and tyrosyl residues brought about AGEs on the basis of synchronous fluorescence spectroscopy have been confirmed. The influence of glycation process on serum albumin binding to 5-dimethylaminonaphthalene-1-sulfonamide (DNSA), 2-(p-toluidino) naphthalene-6-sulfonic acid (TNS), has been studied. Fluorescence analysis showed that environment of both binding site I and II is modified by galactose glycation.

[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 in both bulk soil and clay-size soil fraction, and it was the most major forms in soil organic nitrogen functional groups. Compared with the FALL treatment, the relative proportion of amide/amine-N was lower whereas that of Pyrrole-N was higher in the CK treatment. In the treatments with combined chemical fertilizers and organic manure, the relative proportion of amide/amine-N decreased with increasing application rates of organic manure, while that of Pyrrole-N had an opposite trend. In bulk soil, the relative proportion of amide/amine-N was the highest for the NPKS treatment than for the other treatments. On the other hand, the relative proportion of nitrile/aromatic-N was the highest for the Fallow treatment than for the other treatments in clay-size soil fraction. It is feasible to use N K-edge XANES spectroscopy for characterizing in situ the changes of organic N functional groups in soil under different fertilization practices.

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.

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.

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.

Fate and lability of silver in soils: Effect of ageing

EPA Science Inventory

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the ^110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

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.

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.

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

Effect of reflection and refraction on NEXAFS spectra measured in TEY mode

PubMed Central

2018-01-01

The evolution of near-edge X-ray absorption fine structure in the vicinity of the K-absorption edge of oxygen for HfO2 over a wide range of incidence angles is analyzed by simultaneous implementation of the total-electron-yield (TEY) method and X-ray reflection spectroscopy. It is established that the effect of refraction on the TEY spectrum is greater than that of reflection and extends into the angular region up to angles 2θc. Within angles that are less than the critical angle, both the reflection and refraction strongly distort the shape of the TEY spectrum. Limitations of the technique for the calculation of optical constants from the reflection spectra using the Kramers–Kronig relation in the limited energy region in the vicinity of thresholds are discussed in detail. PMID:29271772

Variability in Chemical Vapor Deposited Zinc Sulfide: Assessment of Legacy and International CVD ZnS Materials

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

McCloy, John S.; Korenstein, Ralph

2009-10-06

Samples of CVD ZnS from the United States, Germany, Israel, and China were evaluated using transmission spectroscopy, x-ray diffraction, photoluminescence, and biaxial flexure testing. Visible and near-infrared scattering, 6 μm absorption, and ultraviolet cut-on edge varied substantially in tested materials. Crystallographic hexagonality and texture was determined and correlated with optical scattering. Transmission cut-on (ultraviolet edge) blue-shifts with annealing and corresponds to visible color but not the 6 μm absorption. Photoluminescence results suggest that CVD ZnS exhibits a complex suite of electronic bandgap defects. All CVD ZnS tested with biaxial flexure exhibit similar fracture strength values and Weibull moduli. This surveymore » suggests that technical understanding of the structure and optical properties CVD ZnS is still in its infancy.« less

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

Ovchinnikova, E. N.; Rogalev, A.; Wilhelm, F.

The local electronic structure of copper ions in a copper metaborate CuB{sub 2}O{sub 4} crystal is studied on the ESRF synchrotron using X-ray absorption polarization-dependent spectroscopy. The X-ray natural circular dichroism near the K absorption edge of copper is measured in the direction that is perpendicular to crystal axis c. The data obtained indicate the presence of hybridized p–d electronic states of copper. Theoretical calculations are used to separate the contributions of the two crystallographically nonequivalent positions of copper atoms in the unit cell of CuB{sub 2}O{sub 4} to the absorption and X-ray circular dichroism spectra of the crystal.

Optical absorption spectra and energy band gap in manganese containing sodium zinc phosphate glasses

NASA Astrophysics Data System (ADS)

Sardarpasha, K. R.; Hanumantharaju, N.; Gowda, V. C. Veeranna

2018-05-01

Optical band gap energy in the system 25Na2O-(75-x)[0.6P2O5-0.4ZnO]-xMnO2 (where x = 0.5,1,5,10 and 20 mol.%) have been studied. The intensity of the absorption band found to increase with increase of MnO2 content. The decrease in the optical band gap energy with increase in MnO2 content in the investigated glasses is attributed to shifting of absorption edge to a longer wavelength region. The obtained results were discussed in view of the structure of phosphate glass network.

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.

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

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

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

Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke

2016-03-07

Here, we evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathodematerials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi 0.5Mn 1.5O 4, the line shape of the Mn L 3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L 3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathodematerials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are usefulmore » enough for the Ni L edge which is far from the O K edge.« less

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.

Towards understanding the electronic structure of Fe-doped CeO2 nanoparticles with X-ray spectroscopy.

PubMed

Wang, Wei-Cheng; Chen, Shih-Yun; Glans, Per-Anders; Guo, Jinghua; Chen, Ren-Jie; Fong, Kang-Wei; Chen, Chi-Liang; Gloter, Alexandre; Chang, Ching-Lin; Chan, Ting-Shan; Chen, Jin-Ming; Lee, Jyh-Fu; Dong, Chung-Li

2013-09-21

This study reports on the electronic structure of Fe-doped CeO2 nanoparticles (NPs), determined by coupled X-ray absorption spectroscopy and X-ray emission spectroscopy. A comparison of the local electronic structure around the Ce site with that around the Fe site indicates that the Fe substitutes for the Ce. The oxygen K-edge spectra that originated from the hybridization between cerium 4f and oxygen 2p states are sensitive to the oxidation state and depend strongly on the concentration of Fe doping. The Ce M(4,5)-edges and the Fe L(2,3)-edges reveal the variations of the charge states of Ce and Fe upon doping, respectively. The band gap is further obtained from the combined absorption-emission spectrum and decreased upon Fe doping, implying Fe doping introduces vacancies. The oxygen vacancies are induced by Fe doping and the spectrum reveals the charge transfer between Fe and Ce. Fe(3+) doping has two major effects on the formation of ferromagnetism in CeO2 nanoparticles. The first, at an Fe content of below 5%, is that the formation of Fe(3+)-Vo-Ce(3+) introduces oxygen deficiencies favoring ferromagnetism. The other, at an Fe content of over 5%, is the formation of Fe(3+)-Vo-Fe(3+), which favors antiferromagnetism, reducing the Ms. The defect structures Fe(3+)-Vo-Ce(3+) and Fe(3+)-Vo-Fe(3+) are crucial to the magnetism in these NPs and the change in Ms can be described as the effect of competitive interactions of magnetic polarons and paired ions.

Adsorption and Reduction of Hexavalent Chromium on the Surface of Vivianite at Acidic Environment

NASA Astrophysics Data System (ADS)

HA, S.; Hyun, S. P.; Lee, W.

2016-12-01

Due to the rapid increase of chemical use in industrial activities, acid spills have frequently occurred in Korea. The acid spill causes soil and water acidification and additional problems such as heavy metal leaching from the soil. Hexavalent chromium (Cr(VI)) is relatively mobile in the environment and toxic and mutagenic. Monoclinic octa-hydrated ferrous phosphate, vivianite, is one of commonly found iron-bearing soil minerals occurring in phosphorous-enriched reducing environments. We have investigated reductive sorption of Cr(VI) on the vivianite surfaces using batch experimental tests under diverse groundwater conditions. Cr(VI) (5 mg/L) was added in 6.5 g/L vivianite suspension buffered at pH 5, 7, and 9, using 0.05 M HEPES or tris buffer solution, to check the effect of pH on the reductive sorption of Cr(VI) on the vivianite surface. The aqueous Cr(VI) removal was fastest at pH 5, followed by pH 7, and pH 9. The effect of ionic strength on the removal kinetics of Cr(VI) was negligible. It could be subsequently removed via sorption and reduction on the surface of vivianite of which reactive chemical species could be aqueous Fe(II), iron oxides, and metavivianite. Adsorption test was conducted using the same amount of Cr(III) to check the selectivity of chromium species on the vivianite surface for the reductive adsorption. Through Cr extraction test, amount of strong-bound Cr to vivianite is similar for Cr(III) and Cr(VI) injection but amount of weak-bound Cr is bigger for Cr(VI) injection. Reaction mechanism for the sorption and reductive transformation of Cr(VI) to Cr(III) species at reactive sites of vivianite surface are discussed based on surface complexation modeling and K-edge Fe X-ray absorption near edge structure (XANES) results. Since vivianite is reacted with Cr(VI), two smooth peaks of absorption edge changed to one sharp peak. Pre-edge that contains 1s-3d transition information tends to show high peak when reaction time is increased and pH is low. This fact indicated that the Fe(II) is oxidized to Fe(III) at the surface of viviante and this phenomena is optimized at pH 5 and longer elapsed time.

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).

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.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

Transport, electronic, and structural properties of nanocrystalline CuAlO2 delafossites

NASA Astrophysics Data System (ADS)

Durá, O. J.; Boada, R.; Rivera-Calzada, A.; León, C.; Bauer, E.; de la Torre, M. A. López; Chaboy, J.

2011-01-01

This work reports on the effect of grain size on the electrical, thermal, and structural properties of CuAlO2 samples obtained by solid-state reaction combined with ball milling. Electrical characterization made in microcrystalline and nanocrystalline samples shows that the electrical conductivity decreases several orders of magnitude for the nanocrystalline samples, and, in addition, there is a large discrepancy between the activation energies associated to thermoelectric power ES. The study of the Cu K-edge x-ray absorption spectra of the CuAlO2 samples shows that the local structure around Cu is preserved after the sintering process, indicating that the observed behavior of the electrical conductivity is of intrinsic origin. Complex conductivity measurements as a function of frequency allow us to discard grain-boundaries effects on the electrical transport. Thus, the changes in σ(T) and S(T) are interpreted in terms of charge localization in the framework of small polarons. This is in agreement with the analysis of the near-edge region of the absorption spectra, which indicates that sintering favors the Cu-O hybridization. As a consequence, oxygen atoms progressively lose their capability of trapping holes, and the electrical conductivity is also enhanced.

Morphology-dependent optical absorption and conduction properties of photoelectrochemical photocatalysts for H2 production: A case study

NASA Astrophysics Data System (ADS)

Huda, Muhammad N.; Turner, John A.

2010-06-01

Efficient photoelectrochemical H2 production by solar irradiation depends not only on the photocatalyst's band gap and its band-edge positions but also on the detailed electronic nature of the bands, such as the localization or delocalization of the band edges and their orbital characteristics. These determine the carrier transport properties, reactivity, light absorption strength, etc. and significantly impact the material's efficiency as a photoconverter. The localization or delocalization of the band edges may arise either due to the orbital nature of the bands or the structural morphology of the material. A recent experimental report on a photocatalyst based on s /p orbitals showed very poor performance for H2 production despite the delocalized nature of the s /p bands as compared to the d-bands of transition metal oxides. It is then important to examine whether this poor performance is inherent to these materials or rather arises from some experimental limitations. A theoretical analysis by first-principle methods is well suited to shed light on this question.

Two-dimensional simulation of GaAsSb/GaAs quantum dot solar cells

NASA Astrophysics Data System (ADS)

Kunrugsa, Maetee

2018-06-01

Two-dimensional (2D) simulation of GaAsSb/GaAs quantum dot (QD) solar cells is presented. The effects of As mole fraction in GaAsSb QDs on the performance of the solar cell are investigated. The solar cell is designed as a p-i-n GaAs structure where a single layer of GaAsSb QDs is introduced into the intrinsic region. The current density–voltage characteristics of QD solar cells are derived from Poisson’s equation, continuity equations, and the drift-diffusion transport equations, which are numerically solved by a finite element method. Furthermore, the transition energy of a single GaAsSb QD and its corresponding wavelength for each As mole fraction are calculated by a six-band k · p model to validate the position of the absorption edge in the external quantum efficiency curve. A GaAsSb/GaAs QD solar cell with an As mole fraction of 0.4 provides the best power conversion efficiency. The overlap between electron and hole wave functions becomes larger as the As mole fraction increases, leading to a higher optical absorption probability which is confirmed by the enhanced photogeneration rates within and around the QDs. However, further increasing the As mole fraction results in a reduction in the efficiency because the absorption edge moves towards shorter wavelengths, lowering the short-circuit current density. The influences of the QD size and density on the efficiency are also examined. For the GaAsSb/GaAs QD solar cell with an As mole fraction of 0.4, the efficiency can be improved to 26.2% by utilizing the optimum QD size and density. A decrease in the efficiency is observed at high QD densities, which is attributed to the increased carrier recombination and strain-modified band structures affecting the absorption edges.

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)

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.

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.

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

Joseph, Kitheri; Stennett, Martin C.; Hyatt, Neil C.

Bulk properties such as glass transition temperature, density and thermal expansion of iron phosphate glass compositions, with replacement of Cs by Ba, are investigated as a surrogate for the transmutation of 137Cs to 137Ba, relevant to the immobilisation of Cs in glass. These studies are required to establish the appropriate incorporation rate of 137Cs in iron phosphate glass. Density and glass transition temperature increases with the addition of BaO indicating the shrinkage and reticulation of the iron phosphate glass network. The average thermal expansion coefficient reduces from 19.8 × 10-6 K-1 to 13.4 × 10-6 K-1, when 25 wt. %more » of Cs2O was replaced by 25 wt. % of BaO in caesium loaded iron phosphate glass. In addition to the above bulk properties, the role of Ba as a network modifier in the structure of iron phosphate glass is examined using various spectroscopic techniques. The FeII content and average coordination number of iron in the glass network was estimated using Mössbauer spectroscopy. The FeII content in the un-doped iron phosphate glass and barium doped iron phosphate glasses was 20, 21 and 22 ± 1% respectively and the average Fe coordination varied from 5.3 ± 0.2 to 5.7 ± 0.2 with increasing Ba content. The atomic scale structure was further probed by Fe K-edge X-ray absorption spectroscopy. The average coordination number provided by extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure was in good agreement with that given by the Mössbauer data.« less

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.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

PubMed

Laguna-Marco, M A; Piquer, C; Roca, A G; Boada, R; Andrés-Vergés, M; Veintemillas-Verdaguer, S; Serna, C J; Iadecola, A; Chaboy, J

2014-09-14

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001)

NASA Astrophysics Data System (ADS)

Ederer, D. L.; Ruzycki, N.; Schuler, T.; Zhang, G. P.; Callcott, T. A.; Nachimuthu, P.; Perera, R. C. C.

2002-03-01

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001) N. Ruzycki^a, T. Schuler^a, D.L. Ederer^a, T. A. Callcott^, G. P. Zhang^b, P. Nachimuthu^c,d, and R.C.C. Perera^c a-Tulane University, Department of Physics, New Orleans, LA, 70118 b- Univesity of Tennessee, Department of Physics and Astronomy, Knoxville, TN, 37996 c- Center for X-ray Optics, Lawrence Berkeley Laboratory, Berkeley, CA, d- Department of Chemistry, University of Nevada Las Vegas, Las Vegas NV, 89154 TiO2 is a useful industrial catalyst and has applications in gas sensing and photoelectric devices. All structures consist of octrahedrally-coordinated Ti atoms and three-fold coordinated O atoms. Anatase and rutile differ mainly in the amount of distortion in the octahedra. Because Soft X-ray Absorption Spectroscoy (SXAS) is sensitive to the ligand field, these small differences are reflected the spectra. In the experiment the electronic polarization vector was varied angulary along the equatorial and the longitudnal axes of the sixfold coordinated titanium atoms. This study showed a strong polarization dependence at the oxygen K-edge for rutile (001) and the anatase (001) in the t_2g and eg region for the equatorial bonds. The Titanium L-edge showed a smaller polarization dependence. There was no polarization dependence in the longitudinal direction for anatase (001) or rutile (001) in either the oxygen K-edge or the Ti-L edge. These data are compared with calculations of polarization-dependent matrix elements of the transitions.

Ultrathin Limit of Exchange Bias Coupling at Oxide Multiferroic/Ferromagnetic Interfaces

DTIC Science & Technology

2013-07-12

perfect, lattice-matched hetero- structures of complex perovskite oxides using state-of-the-art thin fi lm growth techniques has generated new physical...investigated for several BFO/LSMO heterostructures by X-ray absorption spectroscopy (XAS) measurements at 17 K of the Fe- L 2,3 edge at the Advanced Light

Structural and optical properties of lead-boro-tellurrite glasses induced by gamma-ray.

PubMed

Mustafa, Iskandar Shahrim; Kamari, Halimah Mohamed; Yusoff, Wan Mohd Daud Wan; Aziz, Sidek Abdul; Rahman, Azhar Abdul

2013-02-04

Spectrophotometric studies of lead borotellurite glasses were carried out before and after gamma irradiation exposure. The increasing peak on the TeO(4) bi-pyramidal arrangement and TeO(3+1) (or distorted TeO(4)) is due to augmentation of irradiation dose which is attributed to an increase in degree of disorder of the amorphous phase. The structures of lead tellurate contain Pb(3)TeO(6) consisting of TeO(3) trigonal pyramid connected by PbO(4) tetragonal forming a three-dimensional network. The decrease of glass rigidity is due to irradiation process which is supported by the XRD diffractograms results. The decreasing values of absorption edge indicate that red shift effect occur after irradiation processes. A shift in the optical absorption edge attributed to an increase of the conjugation length. The values of optical band gap, E(opt) were calculated and found to be dependent on the glass composition and radiation exposure. Generally, an increase and decrease in Urbach's energy can be considered as being due to an increase in defects within glass network.

The relationship between structural and optical properties of Se-Ge-As glasses

NASA Astrophysics Data System (ADS)

Ghayebloo, M.; Rezvani, M.; Tavoosi, M.

2018-05-01

In this study, the structural and optical characterization of bulk Se-Ge-As glasses has been investigated. In this regards, six different Se60Ge40-xAsx (0 ≤ x ≤ 25) glasses were prepared by conventional melt quenching technique in quartz ampoule. The produced samples were characterized using X-ray diffraction (XRD), Raman spectroscopy, differential thermal analysis (DTA), ultraviolet-visible (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. According to achieved results, fully amorphous phase can easily form in different Se-Ge-As systems. The thermal and optical characteristic of Se60Ge40-xAsx glasses shows anomalous behavior at 5 mol% of As for the glass transition temperature, transmittance, absorption edge, optical energy gap and Urbach energy. The highest glass transition temperature, transmittance, optical energy gap and Urbach energy properties were achieved in Se60Ge35As5 glass as a result of the highest connectivity of cations and anions in glass network.

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.

Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

PubMed

Hao, Yao-Ming; Lou, Shi-Yun; Zhou, Shao-Min; Yuan, Rui-Jian; Zhu, Gong-Yu; Li, Ning

2012-02-02

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.

Structural and Optical Properties of Lead-Boro-Tellurrite Glasses Induced by Gamma-Ray

PubMed Central

Mustafa, Iskandar Shahrim; Kamari, Halimah Mohamed; Yusoff, Wan Mohd Daud Wan; Aziz, Sidek Abdul; Rahman, Azhar Abdul

2013-01-01

Spectrophotometric studies of lead borotellurite glasses were carried out before and after gamma irradiation exposure. The increasing peak on the TeO4 bi-pyramidal arrangement and TeO3+1 (or distorted TeO4) is due to augmentation of irradiation dose which is attributed to an increase in degree of disorder of the amorphous phase. The structures of lead tellurate contain Pb3TeO6 consisting of TeO3 trigonal pyramid connected by PbO4 tetragonal forming a three-dimensional network. The decrease of glass rigidity is due to irradiation process which is supported by the XRD diffractograms results. The decreasing values of absorption edge indicate that red shift effect occur after irradiation processes. A shift in the optical absorption edge attributed to an increase of the conjugation length. The values of optical band gap, Eopt were calculated and found to be dependent on the glass composition and radiation exposure. Generally, an increase and decrease in Urbach’s energy can be considered as being due to an increase in defects within glass network. PMID:23380963

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.

Optical Hydrogen Absorption Consistent with a Thin Bow Shock Leading the Hot Jupiter HD 189733b

NASA Astrophysics Data System (ADS)

Cauley, P. Wilson; Redfield, Seth; Jensen, Adam G.; Barman, Travis; Endl, Michael; Cochran, William D.

2015-09-01

Bow shocks are ubiquitous astrophysical phenomena resulting from the supersonic passage of an object through a gas. Recently, pre-transit absorption in UV metal transitions of the hot Jupiter (HJ) exoplanets HD 189733b and WASP12-b have been interpreted as being caused by material compressed in a planetary bow shock. Here we present a robust detection of a time-resolved pre-transit, as well as in-transit absorption signature around the HJ exoplanet HD 189733b using high spectral resolution observations of several hydrogen Balmer lines. The line shape of the pre-transit feature and the shape of the timeseries absorption provide the strongest constraints on the morphology and physical characteristics of extended structures around an exoplanet. The in-transit measurements confirm the previous exospheric Hα detection, although the absorption depth measured here is ∼50% lower. The pre-transit absorption feature occurs 125 minutes before the predicted optical transit, a projected linear distance from the planet to the stellar disk of 7.2 Rp. The absorption strength observed in the Balmer lines indicates an optically thick, but physically small, geometry. We model this signal as the early ingress of a planetary bow shock. If the bow shock is mediated by a planetary magnetosphere, the large standoff distance derived from the model suggests a large planetary magnetic field strength of Beq = 28 G. Better knowledge of exoplanet magnetic field strengths is crucial to understanding the role these fields play in planetary evolution and the potential development of life on planets in the habitable zone.

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.

Accretion and Structure in the SW Sextantis Stars

NASA Astrophysics Data System (ADS)

Hoard, Donald Wayne

1998-09-01

The SW Sextantis stars are cataclysmic variables (CVs) sharing properties that set them apart from other CVs. These include: strong He II λ4686 emission, velocity curves implying asymmetric disk emission, and variable line profiles displaying a transient absorption feature at specific orbital phases. A number of mechanisms have been proposed to explain these characteristics including (non-disk) circumstellar material, a bipolar disk wind, a white dwarf magnetic field, and coherent accretion stream overflow across the disk, but none has been completely satisfying. I present the results of new photometric and spectroscopic observations of seven SW Sex stars, including Doppler tomogram mapping of emission regions in these systems. These observations, along with recent advances in simulations of accretion disks, suggest a scenario in which the accretion stream undergoes a violent impact with the disk edge. Depending on the mass transfer rate in the stream, the impact site will either cool efficiently (low M) and allow substantial material to flow directly over the disk, or will cool inefficiently (high M) and form a prominent bright spot at the impact site with hot stream material swept 'downstream' along the disk edge. In the former case, non-axisymmetric vertical structure develops in the disk at the terminus of the stream overflow (accounting for absorption seen at φapprox0.5), while in the latter case vertical structure is built up along the disk edge (accounting for absorption at φapprox0.8). The absorption feature phasing in different SW Sex stars implies M decreases as P orb decreases (as expected during CV evolution), but it is not clear whether normal CV evolution can drive changes in M rapidly enough to generate the onset of the SW Sex phenomenon in the narrow range of orbital period they occupy (P orb=3[-]4 hr). I present a gallery of new and archived IUE spectra of the SW Sex stars that display the typically strong UV resonant scattering lines seen in these CVs. The orbital-phase dependence of UV spectral characteristics in UU Aquarii is investigated through a time series of archived IUE spectra, and provides additional evidence of asymmetric structure in this system. The scBINSYN light curve and spectrum modeling package for binary stars has been modified for application to CVs. First results for several SW Sex stars are shown and planned future improvements to the scBINSYN routines are described.

Fe-doping effects on the structural, vibrational, magnetic, and electronic properties of ceria nanoparticles

NASA Astrophysics Data System (ADS)

Aragón, Fermin F. H.; Aquino, Juan C. R.; Ramos, Jesus E.; Coaquira, José A. H.; Gonzalez, Ismael; Macedo, Waldemar A. A.; da Silva, Sebastião W.; Morais, Paulo C.

2017-11-01

In this work, we report on a single-pot synthesis route based on a polymeric precursor method used for successfully producing undoped and iron-doped CeO2 nanoparticles with iron contents up to 10.0 mol. %. The formation of high-crystalline nanoparticles with a cubic fluorite structure is determined for all the studied samples. Meanwhile, the magnetic measurements of the undoped ceria nanoparticles revealed the occurrence of ferromagnetism of bound magnetic polarons of a fraction of Ce3+ at room temperature, and only a paramagnetic behavior of Fe3+ ions was determined for Fe-doped ceria nanoparticles. A monotonous reduction of the effective magnetic moment of the Fe3+ ions was determined. It suggests a change from a high-spin to low-spin state of Fe ions as the Fe content is increased. The 3+ valence state of the iron ions has been confirmed by the Fe K-edge X-ray absorption near-edge structure (XANES) and Mössbauer spectroscopy measurements. X-ray photoelectron spectroscopy data analysis evidenced a coexistence of Ce3+ and Ce4+ ions and a decreasing tendency of the relative fraction of Ce3+ ions in the surface region of the particles as the iron content is increased. Although the coexistence of Ce3+ and Ce4+ is confirmed by results obtained via Ce L3-edge XANES measurements, any clear dependence of the relative relation of Ce3+ ions on the iron content is determined, suggesting a homogeneous distribution of Ce3+ and Ce4+-ions in the whole volume of the particles. Ce L3-edge extended X-ray absorption fine structure revealed that the Ce-O bond distance shows a monotonous decrease as the Fe content is increased, which is in good agreement with the shrinking of the unit cell volume with the iron content determined from XRD data analysis, reinforcing the substitutional solution of Ce and Fe ions in the CeO2 matrix.

Transmission X-ray microscopy for full-field nano-imaging of biomaterials

PubMed Central

ANDREWS, JOY C; MEIRER, FLORIAN; LIU, YIJIN; MESTER, ZOLTAN; PIANETTA, PIERO

2010-01-01

Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full-field transmission X-ray microscopic techniques in the soft and hard X-ray regions. The various capabilities of full-field transmission X-ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X-ray fluorescence and X-ray absorption near edge structure (XANES) imaging. These techniques are discussed and compared in light of results from imaging of biological materials including microorganisms, bone and mineralized tissue and plants, with a focus on hard X-ray TXM at ≤ 40 nm resolution. PMID:20734414

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

Polyakov, B.; Petruhins, A.; Butikova, J.; Kuzmin, A.; Tale, I.

2009-11-01

Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed. in here

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 between formal oxidation state and metal Zeff or, as in the case of [WIV(mdt)2(CO)2], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere. PMID:25068843

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 the difference between formal oxidation state and metal Zeff or, as in the case of [W(IV)(mdt)2(CO)2], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere.

The optical properties of β-FeSi 2 fabricated by ion beam assisted sputtering

NASA Astrophysics Data System (ADS)

McKinty, C. N.; Kewell, A. K.; Sharpe, J. S.; Lourenço, M. A.; Butler, T. M.; Valizadeh, R.; Colligon, J. S.; Reeson Kirkby, K. J.; Homewood, K. P.

2000-03-01

β-FeSi 2 has been shown to have a minimum direct band gap of 0.87 eV [T.D. Hunt, K.J. Reeson, K.P. Homewood, S.W. Teon, R.M. Gwilliam, B.J. Sealy, Nucl. Instr. and Meth. B 84 (1994) 168-171] which leads to the opportunity for Si based opto-electronics, optical communications and optical interconnects. Electroluminescence has been reported from structures containing β-FeSi 2, which were produced by high dose ion implantation and annealing [D. Leong, M.A. Harry, K.J. Reeson, K.P. Homewood, Nature 387 (12 June 1987) 686]. In this paper we report the formation of β-FeSi 2 by ion beam assisted co-sputtering of Fe and Si in varying percentages. The layers were deposited with a varying Fe/Si ratio, with a Si capping layer applied to prevent oxidation. Separate regions of the sample were investigated at room temperature using optical absorption, to measure the band gap values. Absorption under the fundamental edge was also analysed at room temperature. Further investigations looked at the temperature dependence of the band gap and the absorption under the fundamental edge. The results showed that a variety of Fe/Si ratios produced β-FeSi 2, the formation of which was ascertained by the presence of a suitable band gap value [0.83-0.88 eV]. Absorption under the fundamental edge was shown to follow an exponential Urbach tail [C.H. Grein, S. John, Phys. Rev. B 39 (1989) 1140]. The temperature measurements are in good agreement with the Einstein model.

Remarkable optical red shift and extremely high optical absorption coefficient of V-Ga co-doped TiO2

NASA Astrophysics Data System (ADS)

Deng, Quanrong; Han, Xiaoping; Gao, Yun; Shao, Guosheng

2012-07-01

A first attempt has been made to study the effect of codoping of transition metal and sp metal on the electronic structure and associated optical properties of TiO2, through V-Ga codoped thin films. V-Ga codoped rutile TiO2 films were fabricated on fused quartz substrates using pulsed laser ablation, followed by heat treatment at high temperatures. Gigantic redshift in the optical absorption edge was observed in V-Ga co-doped TiO2 materials, from UV to infrared region with high absorption coefficient. Through combined structural characterization and theoretical modeling, this is attributed to the p-d hybridization between the two metals. This leads to additional energy bands to overlap with the minimum of the conduction band, leading to remarkably narrowed band gap free of mid-gap states. The direct-gap of the co-doped phase is key to the remarkably high optical absorption coefficient of the coped titania.

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

Surface Structure of Aerobically Oxidized Diamond Nanocrystals

DOE PAGES

Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; ...

2014-10-27

Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λ excit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton ismore » observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.« less

Surface Structure of Aerobically Oxidized Diamond Nanocrystals

PubMed Central

2015-01-01

We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed. PMID:25436035

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

Computed a multiple band metamaterial absorber and its application based on the figure of merit value

NASA Astrophysics Data System (ADS)

Chen, Chao; Sheng, Yuping; Jun, Wang

2018-01-01

A high performed multiple band metamaterial absorber is designed and computed through the software Ansofts HFSS 10.0, which is constituted with two kinds of separated metal particles sub-structures. The multiple band absorption property of the metamaterial absorber is based on the resonance of localized surface plasmon (LSP) modes excited near edges of metal particles. The damping constant of gold layer is optimized to obtain a near-perfect absorption rate. Four kinds of dielectric layers is computed to achieve the perfect absorption perform. The perfect absorption perform of the metamaterial absorber is enhanced through optimizing the structural parameters (R = 75 nm, w = 80 nm). Moreover, a perfect absorption band is achieved because of the plasmonic hybridization phenomenon between LSP modes. The designed metamaterial absorber shows high sensitive in the changed of the refractive index of the liquid. A liquid refractive index sensor strategy is proposed based on the computed figure of merit (FOM) value of the metamaterial absorber. High FOM values (116, 111, and 108) are achieved with three liquid (Methanol, Carbon tetrachloride, and Carbon disulfide).

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

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.

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

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

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

Yoon, Songhak; Maegli, Alexandra E.; Karvonen, Lassi

Polycrystalline SrTiO{sub 3} and SrTi(O,F){sub 3} powders were synthesized by a solid-state reaction. A partial substitution of oxygen by nitrogen was subsequently carried out using thermal ammonolysis resulting in SrTi(N,O){sub 3} and SrTi(N,O,F){sub 3}. Powder X-ray diffraction (XRD) revealed a cubic perovskite structure with space group Pm-3m for all samples. The thermal ammonolysis slightly increased the lattice parameters, crystallite sizes and strain. As a result from the co-substitution of oxygen with nitrogen and fluorine for SrTi(N,O,F){sub 3}, highly distorted TiO{sub 6} octahedra were detected using X-ray absorption near edge structure (XANES) spectroscopy. The weakening of all active modes of themore » Raman spectra after thermal ammonolysis also indicated enhanced distortions in the local crystal structure. SrTi(N,O,F){sub 3} has the largest amount of nitrogen as well as fluorine among all four samples as determined by thermogravimetric analysis (TGA), elemental analysis and X-ray photoelectron spectroscopy (XPS). In the UV–vis spectra a distinctive shift of the absorption-edge energy was observed exclusively for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. - Graphical abstract: Figure shows the shift of the absorption-edge energy for the SrTi(N,O,F){sub 3} sample from 390 to 510 nm corresponding to a bandgap narrowing from 3.18 to 2.43 eV. Display Omitted - Highlights: • Synthesis of phase-pure SrTi(N,O,F){sub 3} via solid-state reaction. • The incorporated nitrogen contents increase by the presence of fluorine in SrTi(N,O,F){sub 3}. • Co-substitution with nitrogen and fluorine is beneficial for the bandgap narrowing compared to by only nitrogen or fluorine substitution.« less

Advances in Perovskite Solar Cells

PubMed Central

Zuo, Chuantian; Bolink, Henk J.; Han, Hongwei; Huang, Jinsong

2016-01-01

Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite‐based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non‐PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large‐scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed. PMID:27812475

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°.

EDGES result versus CMB and low-redshift constraints on ionization histories

NASA Astrophysics Data System (ADS)

Witte, Samuel; Villanueva-Domingo, Pablo; Gariazzo, Stefano; Mena, Olga; Palomares-Ruiz, Sergio

2018-05-01

We examine the results from the Experiment to Detect the Global Epoch of Reionization Signature (EDGES), which has recently claimed the detection of a strong absorption in the 21 cm hyperfine transition line of neutral hydrogen, at redshifts demarcating the early stages of star formation. More concretely, we study the compatibility of the shape of the EDGES absorption profile, centered at a redshift of z ˜17.2 , with measurements of the reionization optical depth, the Gunn-Peterson optical depth, and Lyman-α emission from star-forming galaxies, for a variety of possible reionization models within the standard Λ CDM framework (that is, a Universe with a cosmological constant Λ and cold dark matter CDM). When, conservatively, we only try to accommodate the location of the absorption dip, we identify a region in the parameter space of the astrophysical parameters that successfully explains all of the aforementioned observations. However, one of the most abnormal features of the EDGES measurement is the absorption amplitude, which is roughly a factor of 2 larger than the maximum allowed value in the Λ CDM framework. We point out that the simple considered astrophysical models that produce the largest absorption amplitudes are unable to explain the depth of the dip and of reproducing the observed shape of the absorption profile.

High resolution x-ray absorption and emission spectroscopy of Li x CoO2 single crystals as a function delithiation

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Iwai, C.; Miyoshi, K.; Takeuchi, J.; Mizokawa, T.; Saini, N. L.

2017-03-01

The effect of delithiation in Li x CoO2 is studied by high resolution Co K-edge x-ray absorption and x-ray emission spectroscopy. Polarization dependence of the x-ray absorption spectra on single crystal samples is exploited to reveal information on the anisotropic electronic structure. We find that the electronic structure of Li x CoO2 is significantly affected by delithiation in which the Co ions oxidation state tending to change from 3+  to 4+. The Co intersite (intrasite) 4p-3d hybridization suffers a decrease (increase) by delithiation. The unoccupied 3d t 2g orbitals with a 1g symmetry, containing substantial O 2p character, hybridize isotropically with Co 4p orbitals and likely to have itinerant character unlike anisotropically hybridized 3d e g orbitals. Such a peculiar electronic structure could have significant effect on the mobility of Li in Li x CoO2 cathode and hence the battery characteristics.

Local structure and defects in ion irradiated KTaO3

NASA Astrophysics Data System (ADS)

Zhang, F. X.; Xi, J.; Zhang, Y.; Tong, Yang; Xue, H.; Huang, R.; Trautmann, C.; Weber, W. J.

2018-04-01

The modification of the local structure in cubic perovskite KTaO3 irradiated with 3 MeV and 1.1 GeV Au ions is studied by Raman and x-ray absorption spectroscopy, complemented by density functional theory (DFT) calculations. In the case of irradiation with 3 MeV Au ions where displacement cascade processes are dominant, the Ta L3-edge x-ray absorption measurements suggest that a peak corresponding to the Ta-O bonds in the TaO6 octahedra splits, which is attributed to the formation of TaK antisite defects that are coupled with oxygen vacancies, V O. This finding is consistent with the DFT calculations. Under irradiation with 1.1 GeV ions, the intense ionization and electronic energy deposition lead to a blue shift and an intensity reduction of active Raman bands. In the case of sequential irradiations, extended x-ray absorption fine structure measurements reveal a decrease in concentration of coupled TaK-V O defects under subsequent irradiation with 1.1 GeV Au ions.

Solid state image sensing arrays

NASA Technical Reports Server (NTRS)

Sadasiv, G.

1972-01-01

The fabrication of a photodiode transistor image sensor array in silicon, and tests on individual elements of the array are described along with design for a scanning system for an image sensor array. The spectral response of p-n junctions was used as a technique for studying the optical-absorption edge in silicon. Heterojunction structures of Sb2S3- Si were fabricated and a system for measuring C-V curves on MOS structures was built.

The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

NASA Astrophysics Data System (ADS)

Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

2017-01-01

Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

DOE PAGES

Wu, M.; Xin, Houlin L.; Wang, J. O.; ...

2018-04-24

Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

2014-01-01

The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

Contrast-enhanced dual-energy subtraction imaging using electronic spectrum-splitting and multi-prism x-ray lenses

NASA Astrophysics Data System (ADS)

Fredenberg, Erik; Cederström, Björn; Lundqvist, Mats; Ribbing, Carolina; Åslund, Magnus; Diekmann, Felix; Nishikawa, Robert; Danielsson, Mats

2008-03-01

Dual-energy subtraction imaging (DES) is a method to improve the detectability of contrast agents over a lumpy background. Two images, acquired at x-ray energies above and below an absorption edge of the agent material, are logarithmically subtracted, resulting in suppression of the signal from the tissue background and a relative enhancement of the signal from the agent. Although promising, DES is still not widely used in clinical practice. One reason may be the need for two distinctly separated x-ray spectra that are still close to the absorption edge, realized through dual exposures which may introduce motion unsharpness. In this study, electronic spectrum-splitting with a silicon-strip detector is theoretically and experimentally investigated for a mammography model with iodinated contrast agent. Comparisons are made to absorption imaging and a near-ideal detector using a signal-to-noise ratio that includes both statistical and structural noise. Similar to previous studies, heavy absorption filtration was needed to narrow the spectra at the expense of a large reduction in x-ray flux. Therefore, potential improvements using a chromatic multi-prism x-ray lens (MPL) for filtering were evaluated theoretically. The MPL offers a narrow tunable spectrum, and we show that the image quality can be improved compared to conventional filtering methods.

Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

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

Wu, M.; Xin, Houlin L.; Wang, J. O.

Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

Optimization of the sources in local hyperthermia using a combined finite element-genetic algorithm method.

PubMed

Siauve, N; Nicolas, L; Vollaire, C; Marchal, C

2004-12-01

This article describes an optimization process specially designed for local and regional hyperthermia in order to achieve the desired specific absorption rate in the patient. It is based on a genetic algorithm coupled to a finite element formulation. The optimization method is applied to real human organs meshes assembled from computerized tomography scans. A 3D finite element formulation is used to calculate the electromagnetic field in the patient, achieved by radiofrequency or microwave sources. Space discretization is performed using incomplete first order edge elements. The sparse complex symmetric matrix equation is solved using a conjugate gradient solver with potential projection pre-conditionning. The formulation is validated by comparison of calculated specific absorption rate distributions in a phantom to temperature measurements. A genetic algorithm is used to optimize the specific absorption rate distribution to predict the phases and amplitudes of the sources leading to the best focalization. The objective function is defined as the specific absorption rate ratio in the tumour and healthy tissues. Several constraints, regarding the specific absorption rate in tumour and the total power in the patient, may be prescribed. Results obtained with two types of applicators (waveguides and annular phased array) are presented and show the faculties of the developed optimization process.

Inelastic losses in X-ray absorption theory

NASA Astrophysics Data System (ADS)

Campbell, Luke Whalin

There is a surprising lack of many body effects observed in XAS (X-ray Absorption Spectroscopy) experiments. While collective excitations and other satellite effects account for between 20% and 40% of the spectral weight of the core hole and photoelectron excitation spectrum, the only commonly observed many body effect is a relatively structureless amplitude reduction to the fine structure, typically no more than a 10% effect. As a result, many particle effects are typically neglected in the XAS codes used to predict and interpret modern experiments. To compensate, the amplitude reduction factor is simply fitted to experimental data. In this work, a quasi-boson model is developed to treat the case of XAS, when the system has both a photoelectron and a core hole. We find that there is a strong interference between the extrinsic and intrinsic losses. The interference reduces the excitation amplitudes at low energies where the core hole and photo electron induced excitations tend to cancel. At high energies, the interference vanishes, and the theory reduces to the sudden approximation. The x-ray absorption spectrum including many-body excitations is represented by a convolution of the one-electron absorption spectrum with an energy dependent spectral function. The latter has an asymmetric quasiparticle peak and broad satellite structure. The net result is a phasor sum, which yields the many body amplitude reduction and phase shift of the fine structure oscillations (EXAFS), and possibly additional satellite structure. Calculations for several cases of interest are found to be in reasonable agreement with experiment. Edge singularity effects and deviations from the final state rule arising from this theory are also discussed. The ab initio XAS code FEFF has been extended for calculations of the many body amplitude reduction and phase shift in x-ray spectroscopies. A new broadened plasmon pole self energy is added. The dipole matrix elements are modified to include a projection operator to calculate deviations from the final state rule and edge singularities.

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

PubMed Central

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

2014-01-01

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

Correlation between bonding structure and microstructure in fullerenelike carbon nitride thin films

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

Gago, R.; Abendroth, B.; Moeller, W.

2005-03-15

The bonding structure of highly ordered fullerenelike (FL) carbon nitride (CN{sub x}) thin films has been assessed by x-ray absorption near-edge spectroscopy (XANES). Samples with different degrees of FL character have been analyzed to discern spectral signatures related to the FL microstructure. The XANES spectra of FL-CN{sub x} films resemble that of graphitic CN{sub x}, evidencing the sp{sup 2} hybridization of both C and N atoms. The FL structure is achieved with the promotion of N in threefold positions over pyridinelike and cyanidelike bonding environments. In addition, the relative {pi}{sup *}/{sigma}* XANES intensity ratio at the C(1s) edge is independentmore » of the FL character, while it decreases {approx}40% at the N(1s) edge with the formation of FL arrangements. This result indicates that there is no appreciable introduction of C-sp{sup 3} hybrids with the development of FL structures and, additionally, that a different spatial localization of {pi} electrons at C and N sites takes place in curved graphitic structures. The latter has implications for the elastic properties of graphene sheets and could, as such, explain the outstanding elastic properties of FL-CN{sub x}.« less

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.

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.

Nanoparticle Filtration in a RTM Processed Epoxy/Carbon Fiber Composite

NASA Technical Reports Server (NTRS)

Miller, Sandi G.; Micham, Logan; Copa, Christine C.; Criss, James M., Jr.; Mintz, Eric A.

2011-01-01

Several epoxy matrix composite panels were fabricated by resin transfer molding (RTM) E862/W resin onto a triaxially braided carbon fiber pre-form. Nanoparticles including carbon nanofiber, synthetic clay, and functionalized graphite were dispersed in the E862 matrix, and the extent of particle filtration during processing was characterized. Nanoparticle dispersion in the resin flashing on both the inlet and outlet edges of the panel was compared by TEM. Variation in physical properties such as Tg and moisture absorption throughout the panel were also characterized. All nanoparticle filled panels showed a decrease in Tg along the resin flow path across the panel, indicating nanoparticle filtration, however there was little change in moisture absorption. This works illustrates the need to obtain good nano-particle dispersion in the matrix resin to prevent particle agglomeration and hence particle filtration in the resultant polymer matrix composites (PMC).

Coordination chemistry of titanium (IV) in silicate glasses and melts: IV. XANES studies of synthetic and natural volcanic glasses and tektites at ambient temperature and pressure

NASA Astrophysics Data System (ADS)

Farges, François; Brown, Gordon E.

1997-05-01

The coordination environment of Ti(IV) in seven natural and synthetic glasses of basaltic, trachytic, rhyolitic composition as well as four tektites has been studied using high-resolution Ti K-edge x-ray absorption near edge structure (XANES) spectroscopy at ambient temperature and pressure. Pre-edge features of Ti K-edge XANES spectra for these glasses suggest that [5]Ti is the dominant Ti coordination in all volcanic glasses. However, in the less polymerized glasses studied (basaltic and trachytic), [6]Ti is also important (30-50% of the total Ti) but [4]Ti was not detected. In contrast, [4]Ti is important in the most polymerized glasses (rhyolites and tektites) (from 30 to 60% of the total Ti depending on NBO/T) with [6]Ti below the detection level (≈10 at%). The local structure around Ti in the natural volcanic glasses is similar to that observed in compositionally similar synthetic silicate glasses and also in Ti-bearing silicate glass and melts with simpler compositions. The presence of F, Cl, and H 2O does not appear to affect the coordination of Ti, based on Ti K-edge XANES measurements of natural glasses bearing these volatile components. In contrast, the presence of nonbridging oxygens (produced by network modifiers) favors [5]Ti in these glass/melts. In parallel, [4]Ti is important when nonbridging oxygens are at small concentrations (NBO/T < 0.1). [6]Ti is detected (i.e., when present >10% of the total Ti) when alkaline-earths are dominant over alkalis, in agreement with bond-valence predictions for Ti-bearing silicate glass/melts below TiO 2 saturation. The abundance of [5]Ti in these silicate glasses (and presumably their melts) is in sharp contrast with the rarity of this Ti coordination state in common rock-forming minerals. Titanium cannot readily enter the structure of most rock-forming minerals, because it is present dominantly as titanyl-bearing ( [5]TiO) units in most natural magmas. In contrast, [6]Ti and [4]Ti (present, respectively, in basic and acidic magmas) are better able to enter inosilicates, but these coordination states represent only a fraction of the Ti in basalts, explaining the usually moderate level of incompatibility of Ti during magmatic differentiation. Finally, [5]Ti transforms to [6]Ti during crystallization of Ti-rich minerals (ilmenite, rutile, pyrochlore).

Metal-ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering

PubMed Central

Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena; Bergmann, Uwe; Wilson, Samuel A.; Glatzel, Pieter; Nordlund, Dennis; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

2013-01-01

Data from Kα resonant inelastic X-ray scattering (RIXS) have been used to extract electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes using an experimentally based theoretical model. Kα RIXS involves resonant 1s → 3d excitation and detection of the 2p → 1s (Kα) emission. This two-photon process reaches similar final states as single-photon L-edge (2p → 3d) X-ray absorption spectroscopy (XAS), but involves only hard X-rays and can therefore be used to get high-resolution L-edge-like spectra for metal proteins, solution catalysts and their intermediates. To analyze the information content of Kα RIXS spectra, data have been collected for four characteristic σ-donor and π-backdonation complexes; ferrous tacn [FeII(tacn)2]Br2, ferrocyanide [FeII(CN)6]K4, ferric tacn [FeIII(tacn)2]Br3 and ferricyanide [FeIII(CN)6]K3. From these spectra metal-ligand covalencies can be extracted using a charge-transfer multiplet model, without previous information from the L-edge XAS experiment. A direct comparison of L-edge XAS and Kα RIXS spectra show that the latter reaches additional final states, e.g., when exciting into the eg (σ*) orbitals, and the splitting between final states of different symmetry provides an extra dimension that makes Kα RIXS a more sensitive probe of σ-bonding. Another key difference between L-edge XAS and Kα RIXS is the π-backbonding features in ferro- and ferricyanide that are significantly more intense in L-edge XAS compared to Kα RIXS. This shows that two methods are complimentary in assigning electronic structure. The Kα RIXS approach can thus be used as a stand-alone method, in combination with L-edge XAS for strongly covalent systems that are difficult to probe by UV/Vis spectroscopy, or as an extension to conventional absorption spectroscopy for a wide range of transition metal enzymes and catalysts. PMID:24131028

Synchrotron WAXS and XANES studies of silica (SiO2) powders synthesized from Indonesian natural sands

NASA Astrophysics Data System (ADS)

Muchlis, Khairanissa; Aini Fauziyah, Nur; Soontaranon, Siriwat; Limpirat, Wanwisa; Pratapa, Suminar

2017-01-01

In this study, we have investigated polymorphic silica (SiO2) powders using, Wide Angle X-ray Scattering (WAXS) and X-Ray Absorption Near Edge Spectroscopy (XANES), laboratory X-Ray Diffraction (XRD) instruments. The WAXS and XANES spectra were collected using synchrotron radiation at Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima, Thailand. The silica powders were obtained by processing silica sand from Tanah Laut, South Kalimantan, Indonesia. Purification process of silica sand was done by magnetic separation and immersion with HCl. The purification step was needed to reduce impurity or undesirable non Si elements. Three polymorphs of silica were produced, i.e. amorphous phase (A), quartz (B), and cristobalite (C). WAXS profile for each phase was presented in terms of intensity vs. 2θ prior to analyses. Both XRD (λCuKα=1.54056 Å) and WAXS (λ=1.09 Å) patttern show that (1) A sample contains no crystallites, (2) B sample is monophasic, contains only quartz, and (3) C sample contains cristobalite and trydimite. XRD quantitative analysis using Rietica gave 98,8 wt% cristobalite, while the associated WAXS data provided 98.7 wt% cristobalite. Si K-edge XANES spectra were measured at energy range 1840 to 1920 eV. Qualitatively, the pre-edge and edge features for all phases are similar, but their main peaks in the post-edge region are different.

Preparation of γ-LiV2O5 from polyoxovanadate cluster Li7[V15O36(CO3)] as a high-performance cathode material and its reaction mechanism revealed by operando XAFS

NASA Astrophysics Data System (ADS)

Wang, Heng; Isobe, Jin; Shimizu, Takeshi; Matsumura, Daiju; Ina, Toshiaki; Yoshikawa, Hirofumi

2017-08-01

γ-phase LiV2O5, which shows superior electrochemical performance as cathode material in Li-ion batteries, was prepared by annealing the polyoxovanadate cluster Li7 [V15O36(CO3)]. The reaction mechanism was studied using operando X-ray absorption fine structure (XAFS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) analyses. The X-ray absorption near edge structure (XANES) and XPS results reveal that γ-LiV2O5 undergoes two-electron redox reaction per V2O5 pyramid unit, resulting in a large reversible capacity of 260 Ah/kg. The extended X-ray absorption fine structure (EXAFS) and PXRD analyses also suggest that the V-V distance slightly increases, due to the reduction of V5+ to V4+ during Li ion intercalation as the material structure is maintained. As a result, γ-LixV2O5 shows highly reversible electrochemical reaction with x = 0.1-1.9.

OPTICAL HYDROGEN ABSORPTION CONSISTENT WITH A THIN BOW SHOCK LEADING THE HOT JUPITER HD 189733B

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

Cauley, P. Wilson; Redfield, Seth; Jensen, Adam G.

Bow shocks are ubiquitous astrophysical phenomena resulting from the supersonic passage of an object through a gas. Recently, pre-transit absorption in UV metal transitions of the hot Jupiter (HJ) exoplanets HD 189733b and WASP12-b have been interpreted as being caused by material compressed in a planetary bow shock. Here we present a robust detection of a time-resolved pre-transit, as well as in-transit absorption signature around the HJ exoplanet HD 189733b using high spectral resolution observations of several hydrogen Balmer lines. The line shape of the pre-transit feature and the shape of the timeseries absorption provide the strongest constraints on themore » morphology and physical characteristics of extended structures around an exoplanet. The in-transit measurements confirm the previous exospheric Hα detection, although the absorption depth measured here is ∼50% lower. The pre-transit absorption feature occurs 125 minutes before the predicted optical transit, a projected linear distance from the planet to the stellar disk of 7.2 R{sub p}. The absorption strength observed in the Balmer lines indicates an optically thick, but physically small, geometry. We model this signal as the early ingress of a planetary bow shock. If the bow shock is mediated by a planetary magnetosphere, the large standoff distance derived from the model suggests a large planetary magnetic field strength of B{sub eq} = 28 G. Better knowledge of exoplanet magnetic field strengths is crucial to understanding the role these fields play in planetary evolution and the potential development of life on planets in the habitable zone.« less

Crystal field splitting and spin states of Co ions in cobalt ferrite with composition Co1.5Fe1.5O4 using magnetization and X-ray absorption spectroscopy measurements

NASA Astrophysics Data System (ADS)

Sinha, A. K.; Singh, M. N.; Achary, S. N.; Sagdeo, A.; Shukla, D. K.; Phase, D. M.

2017-08-01

Structural, magnetic and electronic properties of partially inverted Cobalt Ferrite with composition Co1.5Fe1.5O4 is discussed in the present work. Single phase (SG: Fd3m) sample is synthesized by co-precipitation technique and subsequent air annealing. The values of saturation magnetization obtained from careful analysis of approach to saturation in initial M(H) curves are used to determine spin states of Co ions in tetrahedral (TH) and octahedral (OH) sites. Spin states of Co3+ ions in TH sites, which has not been reported in literature, were found to be in high spin state. Temperature variation of magnetic parameters has been studied. The sample shows magneto-crystalline anisotropy with two clearly distinct pinning centers. Oxygen K-edge and Fe as well as Co L2,3-edge X-ray absorption (XAS) spectra have been used as complementary measurements to study crystal field splitting and core hole effects on transition metal (TM) 3d orbitals. The ratio of intensities of t2g and eg absorption bands in O-K edge XAS spectrum is used to estimate the spin states of Co ions at OH and TH sites. The results are in agreement with those obtained from magnetization data, and favors Co3+ ions in TH sites in high spin states. Normalized areas of the satellite peaks in TM L2,3-edge XAS spectra have been used to estimate 3dn+1L contribution in ground state wave function and the contributions were found to be significant.

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.

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

Specific features of the atomic structure of metallic layers of multilayered (CoFeZr/SiO2)32 and (CoFeZr/ a-Si)40 nanostructures with different interlayers

NASA Astrophysics Data System (ADS)

Domashevskaya, E. P.; Guda, A. A.; Chernyshev, A. V.; Sitnikov, V. G.

2017-02-01

Multilayered nanostructures (MN) were prepared by ion-beam successive sputtering from two targets, one of which was a metallic Co45Fe45Zr10 alloy plate and another target was a quartz (SiO2) or silicon plate on the surface of a rotating glass-ceramic substrate in an argon atmosphere. The Co and Fe K edges X-ray absorption fine structure of XANES in the (CoFeZr/SiO2)32 sample with oxide interlayers was similar to XANES of metallic Fe foil. This indicated the existence in metallic layers of multilayered CoFeZr nanocrystals with a local environment similar to the atomic environment in solid solutions on the base of bcc Fe structure, which is also confirmed by XRD data. XANES near the Co and Fe K edges absorption in another multilayered nanostructure with silicon interlayers (CoFeZr/ a-Si)40 differs from XANES of MN with dielectric SiO2 interlayer, which demonstrates a dominant influence of the Fe-Si and Co-Si bonds in the local environment of 3 d Co and Fe metals when they form CoFeSi-type silicide phases in thinner bilayers of this MN.

Fatigue of LiNi0.8Co0.15Al0.05O2 in commercial Li ion batteries

NASA Astrophysics Data System (ADS)

Kleiner, Karin; Dixon, Ditty; Jakes, Peter; Melke, Julia; Yavuz, Murat; Roth, Christina; Nikolowski, Kristian; Liebau, Verena; Ehrenberg, Helmut

2015-01-01

The degradation of LiNi0.8Co0.15Al0.05O2 (LNCAO), a cathode material in lithium-ion-batteries, was studied using in situ powder diffraction and in situ Ni K edge X-ray absorption spectroscopy (XAS). The fatigued material was taken from a 7 Ah battery which was cycled for 34 weeks under defined durability conditions. Meanwhile, a cell was stored, as reference, under controlled conditions without electrochemical treatment. The fatigued LNCAO used in this study showed a capacity loss of 26% ± 9% compared to the non-cycled material. During charge and discharge the local and the overall structure of LNCAO was investigated by X-ray near edge structure (XANES) analysis, the extended X-ray absorption fine structure (EXAFS) analysis and by using Rietveld refinement of in situ powder diffraction patterns. Both powder diffraction and XAS revealed additional, rhombohedral phases which do not change with electrochemical cycling. Moreover, a phase with the lattice parameters of fully lithiated LNCAO was still present in the fatigued material at high potentials, while it was absent in the non-fatigued reference material. The coexistence of these phases is described by domains within the LNCAO particles, in correlation with the observed fatigue.

Optically induced lattice deformations, electronic structure changes, and enhanced superconductivity in YBa 2Cu 3O 6.48

DOE PAGES

Mankowsky, R.; Fechner, M.; Forst, M.; ...

2017-02-28

Resonant optical excitation of apical oxygen vibrational modes in the normal state of underdoped YBa 2Cu 3O 6+x induces a transient state with optical properties similar to those of the equilibrium superconducting state. Amongst these, a divergent imaginary conductivity and a plasma edge are transiently observed in the photo-stimulated state. Femtosecond hard x-ray diffraction experiments have been used in the past to identify the transient crystal structure in this non-equilibrium state. Here, we start from these crystallographic features and theoretically predict the corresponding electronic rearrangements that accompany these structural deformations. Using density functional theory, we predict enhanced hole-doping of themore » CuO 2 planes. The empty chain Cu dy2-z2 orbital is calculated to strongly reduce in energy, which would increase c-axis transport and potentially enhance the interlayer Josephson coupling as observed in the THz-frequency response. From these results, we calculate changes in the soft x-ray absorption spectra at the Cu L-edge. As a result, femtosecond x-ray pulses from a free electron laser are used to probe changes in absorption at two photon energies along this spectrum and provide data consistent with these predictions.« less

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.

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

Transmission X-ray microscopy for full-field nano imaging of biomaterials.

PubMed

Andrews, Joy C; Meirer, Florian; Liu, Yijin; Mester, Zoltan; Pianetta, Piero

2011-07-01

Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full-field transmission X-ray microscopic techniques in the soft and hard X-ray regions. The various capabilities of full-field transmission X-ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X-ray fluorescence and X-ray absorption near edge structure imaging. These techniques are discussed and compared in light of results from the imaging of biological materials including microorganisms, bone and mineralized tissue, and plants, with a focus on hard X-ray TXM at ≤ 40-nm resolution. Copyright © 2010 Wiley-Liss, Inc.

Synthesis of plant-mediated gold nanoparticles and catalytic role of biomatrix-embedded nanomaterials

PubMed Central

Sharma, Nilesh C.; Nath, Sudip; Parsons, Jason G.; Gardea- Torresdey, Jorge L.; Pal, Tarasankar

2008-01-01

Growth of Sesbania seedlings in chloroaurate solution resulted in the accumulation of gold with the formation of stable gold nanoparticles in plant tissues. Transmission electron microscopy revealed the intracellular distribution of monodisperse nanospheres, possibly due to reduction of the metal ions by secondary metabolites present in cells. X-ray absorption near-edge structure and extended X-ray absorption fine structure demonstrated a high degree of efficiency for the biotransformation of Au(III) into Au(0) by plant tissues. The catalytic function of the nanoparticle-rich biomass was substantiated by the reduction of aqueous 4-nitrophenol (4-NP). This is the first report of gold nanoparticle-bearing biomatrix directly reducing a toxic pollutant, 4-NP. PMID:17711235

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.

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

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe[sub 2] and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

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

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe{sub 2} and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

Combination of first-principles molecular dynamics and XANES simulations for LiCoO2-electrolyte interfacial reactions in a lithium-ion battery

NASA Astrophysics Data System (ADS)

Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

2017-07-01

We performed a first-principles molecular dynamics (FPMD) simulation of the interfacial reactions between a LiCoO2 electrode and a liquid ethylene carbonate (EC) electrolyte. For configurations during the FPMD simulation, we also performed first-principles Co K-edge x-ray absorption near-edge structure (XANES) simulations, which can properly reproduce the bulk and surface spectra of LiCoO2. We observed strong absorption of an EC molecule on the LiCoO2 {110} surface, involving ring opening of the molecule, bond formation between oxygen atoms in the molecule and surface Co ions, and emission of one surface Li ion, while all the surface Co ions remain Co3 +. The surface Co ions having the bond with an oxygen atom in the molecule showed remarkable changes in simulated K-edge spectra which are similar to those of the in situ observation under electrolyte soaking [D. Takamatsu et al., Angew. Chem., Int. Ed. 51, 11597 (2012), 10.1002/anie.201203910]. Thus, the local environmental changes of surface Co ions due to the reactions with an EC molecule can explain the experimental spectrum changes.

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.

Composition and hydrophilicity control of Mn-doped ferrite (MnxFe3-xO4) nanoparticles induced by polyol differentiation.

PubMed

Vamvakidis, Kosmas; Katsikini, Maria; Vourlias, George; Angelakeris, Mavroeidis; Paloura, Eleni C; Dendrinou-Samara, Catherine

2015-03-28

Manganese doped ferrite (MnxFe3-xO4) nanoparticles with x = 0.29-0.77 were prepared under solvothermal conditions in the presence solely of a polyol using the trivalent manganese and iron acetylacetonates as precursors. In this facile approach, a variety of polyols such as polyethylene glycol (PEG 8000), tetraethylene glycol (TEG), propylene glycol (PG) and a mixture of TEG and PG (1 : 1) were utilized in a triple role as a solvent, a reducing agent and a surface-functionalizing agent. The composition of the fine cubic-spinel structures was found to be related to the reductive ability of each polyol, while determination of structural characteristics plus the inversion parameter (i = 0.18-0.38) were provided by X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy at both the Fe and Mn K-edges. The saturation magnetization increased up to 80 emu g(-1) when x = 0.35 and i = 0.22. In addition, the as-prepared nanocrystals coated with PEG, PG and PG&TEG showed excellent colloidal stability in water, while the TEG-coated particles were not water dispersible and converted to hydrophilic when were extra PEGylated. Measurements of the (1)H NMR relaxation in water were carried out and the nanoprobes were evaluated as potential contrast agents.

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

X-Ray Absorption Microspectroscopy with Electrostatic Force Microscopy and its Application to Chemical States Mapping

NASA Astrophysics Data System (ADS)

Ishii, M.; Rigopoulos, N.; Poolton, N. R. J.; Hamilton, B.

2007-02-01

A new technique named X-EFM that measures the x-ray absorption fine structure (XAFS) of nanometer objects was developed. In X-EFM, electrostatic force microscopy (EFM) is used as an x-ray absorption detector, and photoionization induced by x-ray absorption of surface electron trapping sites is detected by EFM. An EFM signal with respect to x-ray photon energy provides the XAFS spectra of the trapping sites. We adopted X-EFM to observe Si oxide thin films. An edge jump shift intrinsic to the X-EFM spectrum was found, and it was explained with a model where an electric field between the trapping site and probe deepens the energy level of the inner-shell. A scanning probe under x-rays with fixed photon energy provided the chemical state mapping on the surface.

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

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

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

ZnO-based transparent conductive thin films via sonicated-assisted sol-gel technique

NASA Astrophysics Data System (ADS)

Malek, M. F.; Mamat, M. H.; Ismail, A. S.; Yusoff, M. M.; Mohamed, R.; Rusop, M.

2018-05-01

We report on the growth of Al-doped ZnO (AZO) thin films onto Corning 7740 glass substrates via sonicated-assisted sol-gel technique. The influence of Al dopant on crystallisation behavior, optical and electrical properties of AZO films has been systematically investigated. All films are polycrystalline with a hexagonal wurtzite structure with a preferential orientation according to the direction <002>. All films exhibit a transmittance above than 80-90 % along the visible range up to 800 nm and a sharp absorption onset below 400 nm corresponding to the fundamental absorption edge of ZnO.

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.

Heat treatment effect on the electronic and magnetic structures of nanographene sheets investigated through electron spectroscopy and conductance measurements.

PubMed

Takashiro, Jun-ichi; Kudo, Yasuhiko; Kaneko, Satoshi; Takai, Kazuyuki; Ishii, Takafumi; Kyotani, Takashi; Enoki, Toshiaki; Kiguchi, Manabu

2014-04-28

The heat treatment effect on the electronic and magnetic structures of a disordered network of nanographene sheets has been investigated by in situ measurements of X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure (NEXAFS), and electrical conductance, together with temperature-programmed desorption measurements. Oxygen-containing functional groups bonded to nanographene edges in the pristine sample are almost completely decomposed under heat treatment up to 1300-1500 K, resulting in the formation of edges primarily terminated by hydrogen. The removal of the oxygen-containing groups enhances the conductance owing to the decrease in the electron transport barriers between nanographene sheets. Heat treatment above 1500 K removes also the hydrogen atoms from the edges, promoting the successive fusion of nanographene sheets at the expense of edges. The decrease in the π* peak width in NEXAFS indicates the progress of the fusion reaction, that is, the extension of the π-conjugation, which agrees with the increase in the orbital susceptibility previously reported. The fusion leads to the formation of local π/sp(2) bridges between nanographene sheets and brings about an insulator-to-metal transition at 1500-1600 K, at which the bridge network becomes infinite. As for the magnetism, the intensity of the edge state peak in NEXAFS, which corresponds to the number of the spin-polarized edge states, decreases above 1500 K, though the effective edge-state spin density per edge state starts decreasing at approximately 200 K lower than the temperature of the edge state peak change. This disagreement indicates the development of antiferromagnetic short range ordering as a precursor of a spin glass state near the insulator-metal transition, at which the random network of inter-nanographene-sheet exchange interactions strengthened with the formation of the π/sp(2) bridges becomes infinite.

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.

Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

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

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

2016-03-23

A systematic X-ray absorption study at actinide N 6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO 2, PuO 2, and UO 3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L 2,3 (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurementsmore » demonstrated an enhanced sensitivity of the N 6,7 spectral shape to changes in the compound crystal structure. Finally, for nonstoichiometric NpO 2-x, the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO 2 which is in agreement with the tentative Np-O phase diagram.« less

The effect of thermal oxidation on the luminescence properties of nanostructured silicon.

PubMed

Liu, Lijia; Sham, Tsun-Kong

2012-08-06

Herein is reported a detailed study of the luminescence properties of nanostructured Si using X-ray excited optical luminescence (XEOL) in combination with X-ray absorption near-edge structures (XANES). P-type Si nanowires synthesized via electroless chemical etching from Si wafers of different doping levels and porous Si synthesized using electrochemical method are examined under X-ray excitation across the Si K-, L(3,2) -, and O K-edges. It is found that while as-prepared Si nanostructures are weak light emitters, intense visible luminescence is observed from thermally oxidized Si nanowires and porous Si. The luminescence mechanism of Si upon oxidation is investigated by oxidizing nanostructured Si at different temperatures. Interestingly, the two luminescence bands observed show different response with the variation of absorption coefficient upon Si and O core-electron excitation in elemental silicon and silicon oxide. A correlation between luminescence properties and electronic structures is thus established. The implications of the finding are discussed in terms of the behavior of the oxygen deficient center (OCD) and non-bridging oxygen hole center (NBOHC). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

DOE PAGES

Sneeden, Eileen Y.; Hackett, Mark J.; Cotelesage, Julien J. H.; ...

2017-07-27

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition tomore » the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.« less

Stellar and Circumstellar Properties of the Pre-Main-Sequence Binary GV Tau from Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Doppmann, Greg W.; Najita, Joan R.; Carr, John S.

2008-09-01

We report spatially resolved spectroscopy of both components of the low-mass pre-main-sequence binary GV Tau. High-resolution spectroscopy in the K and L bands is used to characterize the stellar properties of the binary and to explore the nature of the circumstellar environment. We find that the southern component, GV Tau S, is a radial velocity variable, possibly as a result of an unseen low-mass companion. The strong warm gaseous HCN absorption reported previously by Gibb and coworkers toward GV Tau S was not present during the epoch of our observations. Instead, we detect warm (~500 K) molecular absorption with similar properties toward the northern infrared companion, GV Tau N. At the epoch of our observations, the absorbing gas toward GV Tau N was approximately at the radial velocity of the GV Tau molecular envelope, but it was redshifted with respect to the star by ~13 km s-1. One interpretation of our results is that GV Tau N is also a binary and that most of the warm molecular absorption arises in a circumbinary disk viewed close to edge-on. Data presented herein were obtained at the W. M. Keck Observatory from telescope time allocated to the National Aeronautics and Space Administration through the agency's scientific partnership with the California Institute of Technology and the University of California. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

Experimental determination of the absorption cross-section and molar extinction coefficient of CdSe and CdTe nanowires.

PubMed

Protasenko, Vladimir; Bacinello, Daniel; Kuno, Masaru

2006-12-21

Absorption cross-sections and corresponding molar extinction coefficients of solution-based CdSe and CdTe nanowires (NWs) are determined. Chemically grown semiconductor NWs are made via a recently developed solution-liquid-solid (SLS) synthesis, employing low melting Au/Bi bimetallic nanoparticle "catalysts" to induce one-dimensional (1D) growth. Resulting wires are highly crystalline and have diameters between 5 and 12 nm as well as lengths exceeding 10 microm. Narrow diameters, below twice the corresponding bulk exciton Bohr radius of each material, place CdSe and CdTe NWs within their respective intermediate to weak confinement regimes. Supporting this are solution linear absorption spectra of NW ensembles showing blue shifts relative to the bulk band gap as well as structure at higher energies. In the case of CdSe, the wires exhibit band edge emission as well as strong absorption/emission polarization anisotropies at the ensemble and single-wire levels. Analogous photocurrent polarization anisotropies have been measured in recently developed CdSe NW photodetectors. To further support fundamental NW optical/electrical studies as well as to promote their use in device applications, experimental absorption cross-sections are determined using correlated transmission electron microscopy, UV/visible extinction spectroscopy, and inductively coupled plasma atomic emission spectroscopy. Measured CdSe NW cross-sections for 1 microm long wires (diameters, 6-42 nm) range from 6.93 x 10(-13) to 3.91 x 10(-11) cm2 at the band edge (692-715 nm, 1.73-1.79 eV) and between 3.38 x 10(-12) and 5.50 x 10(-11) cm2 at 488 nm (2.54 eV). Similar values are obtained for 1 microm long CdTe NWs (diameters, 7.5-11.5 nm) ranging from 4.32 x 10(-13) to 5.10 x 10(-12) cm2 at the band edge (689-752 nm, 1.65-1.80 eV) and between 1.80 x 10(-12) and 1.99 x 10(-11) cm2 at 2.54 eV. These numbers compare well with previous theoretical estimates of CdSe/CdTe NW cross-sections far to the blue of the band edge, having order of magnitude values of 1.0 x 10(-11) cm2 at 488 nm. In all cases, experimental NW absorption cross-sections are 4-5 orders of magnitude larger than those for corresponding colloidal CdSe and CdTe quantum dots. Even when volume differences are accounted for, band edge NW cross-sections are larger by up to a factor of 8. When considered along with their intrinsic polarization sensitivity, obtained NW cross-sections illustrate fundamental and potentially exploitable differences between 0D and 1D materials.

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).