Sample records for k-edge exafs studies

  1. 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.

  2. 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.

  3. 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.

  4. Ti K-edge EXAFS and XANES study on tektites from different strewnfields

    NASA Astrophysics Data System (ADS)

    Wang, L.; Furuta, T.; Okube, M.; Yoshiasa, A.

    2011-12-01

    The concentration and local structure of each element may have various kinds of information about the asteroid impact and mass extinction. Farges and Brown have discussed about the Ti local structure by XANES, and concluded that Ti in tektite occupies 4-coordinated site. EXAFS can be analyzed to give precise information about the distance from Ti to near neighbors. The XAFS measurement of Ti local structure was preformed at the beamline 9C of the Photon Factory in KEK, Tsukuba, Japan. The specimens of tektites are from different strewnfields, they are: indochinite, bediasite, hainanite, philippinite, australite and moldavite. Sample for comparison are Libya desert glass and suevite. The k3χ(k) function was transformed into the radial structure function (RSF) for Ti K-edge of six tektites. The RSF for the Ti atom in indochinite and bediasite are similar; hainanite, australite and philippinite are similar; and moldavite is discriminated from others. It indicates that they have the same local atomic environmental around the Ti atoms and extended structure respectively. Coordination numbers and radial structure function are determined by EXAFS analyses (Table 1). We classified the tektites in three types: in indochinite and bediasite, Ti occupies 4-coordinated tetrahedral site and Ti-O distances are 1.84-1.81 Å; in hainanite, australite and philippinite, Ti occupies 5-coordinated trigonal bi-pyramidal or tetragonal pyramidal site and Ti-O distances are 1.92-1.87 Å; in moldavite, Ti occupies the 6-coordinated octahedral site and Ti-O distance is 2.00-1.96 Å. Formation of tektites is related to the impact process. It is generally recognized that tektites were formed under higher temperature and high pressure. But through this study, local structures of Ti are differing in three strewnfields and even different locations of the same strewnfield. What caused the various local structures will be another topic of tektite studies. Local structure of Ti may be changed in

  5. Bayes-Turchin Analysis of Overlapping L-Edges EXAFS Data of Iron

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

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

    2007-02-02

    Spin polarized and spin averaged extended x-ray absorption fine structure ((M)EXAFS) data were measured at temperatures of 180 K and 296 K in the soft x-ray energy regime of the overlapping L-edges of an iron film grown on V(110). The absorption coefficients were analyzed with the Bayes-Turchin procedure. The analysis yields the correction function to the atomic-like background-absorption coefficient calculated by FEFF8 and reveals components of atomic EXAFS oscillations. The EXAFS Debye-Waller (DW) parameters were determined. Their split into a thermal and a structural contribution was not possible without theoretical input since the two temperatures in this experiment were notmore » sufficiently far apart from each other and the k range of the data was too small. The a priori values of the thermal contribution to the DW parameters were therefore derived from a force-field model with two spring constants. They were adjusted to DW parameters calculated from Born-von Karman force constants which had been obtained from inelastic neutron scattering. Those two spring constants also nicely reproduce the unprojected vibrational density of states deduced from phonon dispersion curves. The MEXAFS oscillations can be described by the rigid-band model and the L2- and L3-EXAFS components. A negative exchange-related energy is obtained by fitting the MEXAFS signal in the extended energy region. This is in contrast to the predictions of the Hedin-Lundquist functional and the Dirac-Hara functional used in the FEFF8 code.« less

  6. 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.

  7. 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.

  8. X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

    NASA Astrophysics Data System (ADS)

    Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

    2017-05-01

    Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

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

    PubMed

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

    2005-07-14

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

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

    PubMed Central

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

    2016-01-01

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

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

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

    Yang, Jianjun; Wang, Jian; Pan, Weinan

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

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

    DOE PAGES

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

    2016-05-23

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

  13. 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.

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

    PubMed Central

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

    2014-01-01

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

  15. 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.

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1990-01-01

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

  17. Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

    NASA Astrophysics Data System (ADS)

    Furnare, Luca J.; Vailionis, Arturas; Strawn, Daniel G.

    2005-11-01

    Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength ( I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

  19. 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.

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

    PubMed Central

    2015-01-01

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

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

    PubMed

    Leto, Domenick F; Jackson, Timothy A

    2014-06-16

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

  2. 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.

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

    PubMed

    Medling, Scott; Bridges, Frank

    2011-07-01

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

  4. 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

  5. X-ray source development for EXAFS measurements on the National Ignition Facility.

    PubMed

    Coppari, F; Thorn, D B; Kemp, G E; Craxton, R S; Garcia, E M; Ping, Y; Eggert, J H; Schneider, M B

    2017-08-01

    Extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first time on the NIF laser, and the requirements for optimization have been established.

  6. X-ray source development for EXAFS measurements on the National Ignition Facility

    DOE PAGES

    Coppari, F.; Thorn, D. B.; Kemp, G. E.; ...

    2017-08-28

    We present that extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. Finally, EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first timemore » on the NIF laser, and the requirements for optimization have been established.« less

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

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

    PubMed

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

    2010-06-01

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

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

    PubMed

    Atak, Haluk; Shikhaliev, Polad M

    2016-03-01

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

  10. 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

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

    PubMed

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

    2017-06-19

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

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

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

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

  14. 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.

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

    PubMed

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

    2012-04-28

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

  16. EXAFS study of some coordination polymers of copper

    NASA Astrophysics Data System (ADS)

    Deshpande, A. P.

    1995-02-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

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

    USGS Publications Warehouse

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

    2004-01-01

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

  20. 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.

  1. 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.

  2. Carbon K-edge spectra of carbonate minerals.

    PubMed

    Brandes, Jay A; Wirick, Sue; Jacobsen, Chris

    2010-09-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

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

    USGS Publications Warehouse

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

    1995-01-01

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

  4. 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.

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

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

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

    2015-06-24

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

  6. 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.

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

    PubMed

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

    2017-06-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

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

    PubMed Central

    Sarangi, Ritimukta

    2012-01-01

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

  13. 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

  14. 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.

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

    PubMed

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

    2012-09-21

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

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

    PubMed

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

    2006-03-15

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

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

    USGS Publications Warehouse

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

    1993-01-01

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

  18. 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.

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

    PubMed

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

    2013-09-25

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

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

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

    Westre, Tami E.

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

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2001-09-01

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

  3. 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

  4. 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

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

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

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

    2007-02-02

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

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

    NASA Astrophysics Data System (ADS)

    Moon, Ellen M.; Peacock, Caroline L.

    2011-11-01

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

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

    PubMed

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

    2017-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Joyner, Richard W.

    1980-05-01

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

  9. 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.

  10. Spectral K-edge subtraction imaging

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  11. Investigating the interstellar dust through the Fe K-edge

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

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

    USGS Publications Warehouse

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

    2005-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  15. 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

  16. 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

  17. 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

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

    PubMed

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

    2002-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  1. 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.

  2. 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.

  3. EXAFS studies of prostate cancer cell lines

    NASA Astrophysics Data System (ADS)

    Czapla, J.; Kwiatek, W. M.; Lekki, J.; Kisiel, A.; Steininger, R.; Goettlicher, J.

    2013-04-01

    Sulphur plays a vital role in every human organism. It is known, that sulphur-bearing compounds, such as for example cysteine and glutathione, play critical roles in development and progression of many diseases. Any alteration in sulphur's biochemistry could become a precursor of serious pathological conditions. One of such condition is prostate cancer, the most frequently diagnosed malignancy in the western world and the second leading cause of cancer related death in men. The purpose of presented studies was to examine what changes occur in the nearest chemical environment of sulphur in prostate cancer cell lines in comparison to healthy cells. The Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used, followed by theoretical calculations. The results of preliminary analysis is presented.

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

    NASA Astrophysics Data System (ADS)

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

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

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    USGS Publications Warehouse

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

    1996-01-01

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

  8. 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.

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

    PubMed

    Tommaseo, C E; Kersten, M

    2002-07-01

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

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  12. 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

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

    NASA Astrophysics Data System (ADS)

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

    1989-07-01

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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2001-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  17. 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

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

    PubMed

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

    2017-04-01

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

  19. 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

  20. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

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

    PubMed

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

    2014-11-01

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

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

    PubMed

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

    2016-01-21

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

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

    PubMed

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

    2018-05-01

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

  5. An EXAFS study on the so-called {open_quotes}Co-Mo-S{close_quotes} phase in Co/C and CoMo/C, compared with a Moessbauer emission spectroscopy study

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

    Craje, M.W.J.; Kraan, A.M. van der; Louwers, S.P.A.

    1992-06-25

    EXAFS was used in this paper to study 4 sulfided catalysts that have the same structure as their {sup 57}Co counterparts characterized by Mossbauer emission spectroscopy. The {open_quotes}Co-Mo-S{close_quotes} phase in Co/C is similar to CoMo/C due to a very highly dispersed Co species. Without Mo, the sulfidic Co results in a Co{sub 9}S{sub 8} phase during sulfidation at 673K, Mo prevents Co sintering in CoMo/C. 37 refs., 6 figs., 2 tabs.

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

    NASA Astrophysics Data System (ADS)

    Peacock, Caroline L.; Sherman, David M.

    2004-06-01

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

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

    ERIC Educational Resources Information Center

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

    2007-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Vespa, M.; Dähn, R.; Wieland, E.

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

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

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

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

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

  10. 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.

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

    PubMed

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

    2012-01-16

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

  12. 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.

  13. 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

  14. Studies on effective atomic numbers, electron densities from mass attenuation coefficients near the K edge in some samarium compounds.

    PubMed

    Akman, F; Durak, R; Turhan, M F; Kaçal, M R

    2015-07-01

    The effective atomic numbers and electron densities of some samarium compounds were determined using the experimental total mass attenuation coefficient values near the K edge in the X-ray energy range from 36.847 up to 57.142 keV. The measurements, in the region from 36.847 to 57.142 keV, were done in a transmission geometry utilizing the Kα2, Kα1, Kβ1 and Kβ2 X-rays from different secondary source targets excited by the 59.54 keV gamma-photons from an Am-241 annular source. This paper presents the first measurement of the effective atomic numbers and electron densities for some samarium compounds near the K edge. The results of the study showed that the measured values were in good agreement with the theoretically calculated ones. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

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

    Jensen, T.; Whitmore, C.

    1999-01-05

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

  16. Large local disorder in superconducting K(0.8)Fe(1.6)Se2 studied by extended x-ray absorption fine structure.

    PubMed

    Iadecola, A; Joseph, B; Simonelli, L; Puri, A; Mizuguchi, Y; Takeya, H; Takano, Y; Saini, N L

    2012-03-21

    We have measured the local structure of superconducting K(0.8)Fe(1.6)Se(2) chalcogenide (T(c) = 31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for the Fe-Se bondlength (k ~ 5.8 eV Å(-2)) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to be flexible (k ~ 2.1 eV Å(-2)) in comparison to the binary FeSe (k ~ 3.5 eV Å(-2)), an indication of partly relaxed Fe-Fe networks in K(0.8)Fe(1.6)Se(2). The results suggest a glassy nature for the title system, with the superconductivity being similar to that in the granular materials. © 2012 IOP Publishing Ltd

  17. XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

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

    Robblee, John Henry

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S 3 → [S 4] → S 0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electronmore » paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S 2 → S 3 transition, in contrast to the S 0 → S 1 and S 1 → S 2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S 2 → S 3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S 0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S 1} state to 2.85 Å in the S 0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn 2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S 0 state have been investigated and a characteristic ''multiline'' signal in the S 0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S 0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S 0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds

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

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  20. 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.

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

    PubMed Central

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

    2013-01-01

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

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

    DOE PAGES

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

    2017-05-08

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-10-01

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

  4. Studies of EXAFSSpectra using Copper (II) Schiff Base complexes and Determination of Bond lengths Using Synchrotron Radiation

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Vibhute, V.; Ninama, S.; Parsai, N.; Jha, S. N.; Sharma, P.

    2016-10-01

    X-ray absorption fine structure (XAFS) at the K-edge of copper has been studied in some copper (II) complexes with substituted anilines like (2Cl, 4Br, 2NO2, 4NO2 and pure aniline) with o-PDA (orthophenylenediamine) as ligand. The X-ray absorption measurements have been performed at the recently developed BL-8 dispersive EXAFS beam line at 2.5 GeV Indus-2 Synchrotron Source at RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena.The graphical method gives the useful information about bond length and also the environment of the absorbing atom. The theoretical bond lengths of the complexes were calculated by using interactive fitting of EXAFS using fast Fourier inverse transformation (IFEFFIT) method. This method is also called as Fourier transform method. The Lytle, Sayers and Stern method and Levy's method have been used for determination of bond lengths experimentally of the studied complexes. The results of both methods have been compared with theoretical IFEFFIT method.

  5. Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

    NASA Astrophysics Data System (ADS)

    Padovani, S.; Borgia, I.; Brunetti, B.; Sgamellotti, A.; Giulivi, A.; D'Acapito, F.; Mazzoldi, P.; Sada, C.; Battaglin, G.

    Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface.

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

  7. 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.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  13. 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.

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

    PubMed

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

    2010-11-11

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

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

    NASA Astrophysics Data System (ADS)

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

    1996-05-01

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

  16. 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

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

    PubMed Central

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

    2017-01-01

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

  18. Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Mo, Yibo

    In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

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

    PubMed

    Ziemba, Brian P; Falke, Joseph J

    2018-01-01

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

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

    PubMed Central

    Ziemba, Brian P.

    2018-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

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

    PubMed

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

    2015-12-07

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

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

    PubMed

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

    2013-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-11-01

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

  8. 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

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

    PubMed Central

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

    2004-01-01

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

  10. 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.

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

    PubMed

    Gu, Weiwei; Wang, Hongxin; Wang, Kun

    2014-05-07

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

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

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

    PubMed

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

    2015-05-27

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

  16. Silicon Detector System for High Rate EXAFS Applications.

    PubMed

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

    1995-08-01

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

  17. Silicon Detector System for High Rate EXAFS Applications

    PubMed Central

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

    2015-01-01

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

  18. Polarization-dependent DANES study on vertically-aligned ZnO nanorods

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

    Sun, Chengjun; Park, Chang-In; Jin, Zhenlan

    2016-05-01

    The local structural and local density of states of vertically-aligned ZnO nanorods were examined by using a polarization-dependent diffraction anomalous near edge structure (DANES) measurements from c-oriented ZnO nanorods at the Zn K edge with the incident x-ray electric field parallel and perpendicular to the x-ray momentum transfer direction. Orientation-dependent local structures determined by DANES were comparable with polarization-dependent EXAFS results. Unlike other techniques, polarization-dependent DANES can uniquely describe the orientation-dependent local structural properties and the local density of states of a selected element in selected-phased crystals of compounds or mixed-phased structures.

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

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

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

    2016-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Jiang, Yu

    2009-12-01

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

  1. Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

    PubMed

    Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

    2011-07-04

    The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

  2. 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

  3. EXAFS and XANES analysis of oxides at the nanoscale.

    PubMed

    Kuzmin, Alexei; Chaboy, Jesús

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

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

    PubMed

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

    2013-10-07

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

  6. Arsenic Scavenging by Al-Substituted Ferrihydrites in a Circumneutral pH River Impacted by the Acid Mine Drainage of Carnoulès, Gard, France

    NASA Astrophysics Data System (ADS)

    ADRA, A.; Morin, G.; ona-Nguema, G.; Maillot, F.; Casiot, C.; Bruneel, O.

    2013-12-01

    Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure and reactivity of aluminum-rich Fh from river-bed sediments collected in a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. EXAFS analysis indicates that Al(III) substitutes for Fe(III) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 20-37×7 mol%Al range, in agreement with bulk chemical compositions. Synthetic aluminous Fh analogues prepared in the present study are found to be less Al-substituted (14-18×4 mol%Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidences for the scavenging of arsenic by natural Al- Fh, with possible implications for other pollutants in natural or engineered systems.

  7. 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.

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

    PubMed

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

    2011-09-01

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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  11. 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

  12. 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.

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

    PubMed

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

    2013-07-01

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

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

    PubMed Central

    2015-01-01

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

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

    PubMed

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

    2013-04-16

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

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

    DOE PAGES

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

    2015-10-23

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

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1989-07-01

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

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

    PubMed

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

    2014-06-28

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

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

    PubMed

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

    2014-10-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

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

  3. 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.

  4. A Monte Carlo simulation study of an improved K-edge log-subtraction X-ray imaging using a photon counting CdTe detector

    NASA Astrophysics Data System (ADS)

    Lee, Youngjin; Lee, Amy Candy; Kim, Hee-Joung

    2016-09-01

    Recently, significant effort has been spent on the development of photons counting detector (PCD) based on a CdTe for applications in X-ray imaging system. The motivation of developing PCDs is higher image quality. Especially, the K-edge subtraction (KES) imaging technique using a PCD is able to improve image quality and useful for increasing the contrast resolution of a target material by utilizing contrast agent. Based on above-mentioned technique, we presented an idea for an improved K-edge log-subtraction (KELS) imaging technique. The KELS imaging technique based on the PCDs can be realized by using different subtraction energy width of the energy window. In this study, the effects of the KELS imaging technique and subtraction energy width of the energy window was investigated with respect to the contrast, standard deviation, and CNR with a Monte Carlo simulation. We simulated the PCD X-ray imaging system based on a CdTe and polymethylmethacrylate (PMMA) phantom which consists of the various iodine contrast agents. To acquired KELS images, images of the phantom using above and below the iodine contrast agent K-edge absorption energy (33.2 keV) have been acquired at different energy range. According to the results, the contrast and standard deviation were decreased, when subtraction energy width of the energy window is increased. Also, the CNR using a KELS imaging technique is higher than that of the images acquired by using whole energy range. Especially, the maximum differences of CNR between whole energy range and KELS images using a 1, 2, and 3 mm diameter iodine contrast agent were acquired 11.33, 8.73, and 8.29 times, respectively. Additionally, the optimum subtraction energy width of the energy window can be acquired at 5, 4, and 3 keV for the 1, 2, and 3 mm diameter iodine contrast agent, respectively. In conclusion, we successfully established an improved KELS imaging technique and optimized subtraction energy width of the energy window, and based on

  5. A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

    PubMed

    Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

    2007-07-01

    A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

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

    PubMed

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

    2016-12-01

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

  7. Arsenic scavenging by aluminum-substituted ferrihydrites in a circumneutral pH river impacted by acid mine drainage.

    PubMed

    Adra, Areej; Morin, Guillaume; Ona-Nguema, Georges; Menguy, Nicolas; Maillot, Fabien; Casiot, Corinne; Bruneel, Odile; Lebrun, Sophie; Juillot, Farid; Brest, Jessica

    2013-11-19

    Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure of aluminum-rich Fh, and their role in arsenic scavenging in river-bed sediments from a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. TEM-EDXS elemental mapping and SEM-EDXS analyses combined with EXAFS analysis indicates that Al(3+) substitutes for Fe(3+) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 25-30 ± 10 mol %Al range. Synthetic aluminous Fh prepared in the present study are found to be less Al-substituted (14-20 ± 5 mol %Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidence for the scavenging of arsenic by natural Al-Fh, which emphasize the possible implication of such material for scavenging pollutants in natural or engineered systems.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

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

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

    Chen, H; Cormack, R; Bhagwat, M

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

  11. Portable X-Ray, K-Edge Heavy Metal Detector

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

    Fricke, V.

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

  12. EXAFS and electrical studies of new narrow-gap semiconductors: InTe1-xSex and In1-xGaxTe

    NASA Astrophysics Data System (ADS)

    Lebedev, A. I.; Michurin, A. V.; Sluchinskaya, I. A.; Demin, V. N.; Munro, I. H.

    2000-12-01

    The local environment of Ga, Se and Tl atoms in InTe-based solid solutions was studied by EXAFS technique. It was shown that all investigated atoms are substitutional impurities, which enter the In(1), Te and In(2) positions in the InTe structure, respectively. The electrical measurements revealed that In1-xGaxTe and InTe1-xSex solid solutions become semiconductors at x>0.24 and >0.15, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  14. 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

  15. 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

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

    NASA Astrophysics Data System (ADS)

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

    1998-09-01

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

  17. 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.

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

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

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

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

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

    DOE PAGES

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

    2018-01-31

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

  20. Observation of yttrium oxide nanoparticles in cabbage (Brassica oleracea) through dual energy K-edge subtraction imaging

    DOE PAGES

    Chen, Yunyun; Sanchez, Carlos; Yue, Yuan; ...

    2016-03-25

    Background: The potential transfer of engineered nanoparticles (ENPs) from plants into the food chain has raised widespread concerns. In order to investigate the effects of ENPs on plants, young cabbage plants (Brassica oleracea) were exposed to a hydroponic system containing yttrium oxide (yttria) ENPs. The objective of this study was to reveal the impacts of NPs on plants by using K-edge subtraction imaging technique. Results: Using synchrotron dual-e nergy X-ray micro-tomography with K-edge subtraction technique, we studied the uptake, accumulation, distribution and concentration mapping of yttria ENPs in cabbage plants. It was found that yttria ENPs were uptaken by themore » cabbage roots but did not effectively transferred and mobilized through the cabbage stem and leaves. This could be due to the accumulation of yttria ENPs blocked at primary-lateral-root junction. Instead, non-yttria minerals were found in the xylem vessels of roots and stem. Conclusions: Synchrotron dual-energy X-ray micro-tomography is an effective method to observe yttria NPs inside the cabbage plants in both whole body and microscale level. Furthermore, the blockage of a plant's roots by nanoparticles is likely the first and potentially fatal environmental effect of such type of nanoparticles.« less

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Identification of jasmine flower (Jasminum sp.) based on the shape of the flower using sobel edge and k-nearest neighbour

    NASA Astrophysics Data System (ADS)

    Qur’ania, A.; Sarinah, I.

    2018-03-01

    People often wrong in knowing the type of jasmine by just looking at the white color of the jasmine, while not all white flowers including jasmine and not all jasmine flowers have white. There is a jasmine that is yellow and there is a jasmine that is white and purple.The aim of this research is to identify Jasmine flower (Jasminum sp.) based on the shape of the flower image-based using Sobel edge detection and k-Nearest Neighbor. Edge detection is used to detect the type of flower from the flower shape. Edge detection aims to improve the appearance of the border of a digital image. While k-Nearest Neighbor method is used to classify the classification of test objects into classes that have neighbouring properties closest to the object of training. The data used in this study are three types of jasmine namely jasmine white (Jasminum sambac), jasmine gambir (Jasminum pubescens), and jasmine japan (Pseuderanthemum reticulatum). Testing of jasmine flower image resized 50 × 50 pixels, 100 × 100 pixels, 150 × 150 pixels yields an accuracy of 84%. Tests on distance values of the k-NN method with spacing 5, 10 and 15 resulted in different accuracy rates for 5 and 10 closest distances yielding the same accuracy rate of 84%, for the 15 shortest distance resulted in a small accuracy of 65.2%.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  7. 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.

  8. Synchrotron-based intra-venous K-edge digital subtraction angiography in a pig model: a feasibility study.

    PubMed

    Schültke, Elisabeth; Fiedler, Stefan; Nemoz, Christian; Ogieglo, Lissa; Kelly, Michael E; Crawford, Paul; Esteve, Francois; Brochard, Thierry; Renier, Michel; Requardt, Herwig; Le Duc, Geraldine; Juurlink, Bernhard; Meguro, Kotoo

    2010-03-01

    K-edge digital subtraction angiography (KEDSA) combined with the tunability of synchrotron beam yields an imaging technique that is highly sensitive to low concentrations of contrast agents. Thus, contrast agent can be administered intravenously, obviating the need for insertion of a guided catheter to deliver a bolus of contrast agent close to the target tissue. With the high-resolution detectors used at synchrotron facilities, images can be acquired at high spatial resolution. Thus, the KEDSA appears particularly suited for studies of neurovascular pathology in animal models, where the vascular diameters are significantly smaller than in human patients. This feasibility study was designed to test the suitability of KEDSA after intravenous injection of iodine-based contrast agent for use in a pig model. Four adult male pigs were used for our experiments. Neurovascular angiographic images were acquired using KEDSA with a solid state Germanium (Ge) detector at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. After intravenous injection of 0.9 ml/kg iodinated contrast agent (Xenetix), the peak iodine concentrations in the internal carotid and middle cerebral arteries reached 35 mg/ml. KEDSA images in radiography mode allowed the visualization of intracranial arteries of less than 1.5mm diameter. Copyright 2009 Elsevier Ireland Ltd. All rights reserved.

  9. Fe K-edge XANES of Maya blue pigment

    NASA Astrophysics Data System (ADS)

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

    2005-08-01

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

  10. 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

  11. Structural investigations in helium charged titanium films using grazing incidence XRD and EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Wan, Chubin; Zhou, Xiaosong; Wang, Yuting; Li, Shina; Ju, Xin; Peng, Shuming

    2014-01-01

    The crystal structure and local atomic arrangements surrounding Ti atoms were determined for He-charged hexagonal close-packed (hcp) Ti films and measured at glancing angles by synchrotron radiation X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively. The charged specimens were prepared by direct current magnetron sputtering with a He/Ar mixture. He atoms with a relatively medium concentration (He/Ti atomic ratio as high as 17 at.%) were incorporated evenly in the deposited films. XRD results showed the changes in the peak intensities in Ti films with different He contents. EXAFS Fourier Transform analysis indicated that the average Ti-Ti distance decreased significantly, and proved the existence of phase transition.

  12. Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  13. Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

    NASA Technical Reports Server (NTRS)

    Richmond, Robert C.; Frigo, Sean P.; Ehret, Charles F.; Rose, M. Franklin (Technical Monitor)

    2001-01-01

    This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

  14. Wide angle X-ray scattering (WAXS) study of "two-line" ferrihydrite structure: Effect of arsenate sorption and counterion variation and comparison with EXAFS results

    USGS Publications Warehouse

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

    1996-01-01

    small "sheet" units. Analysis of the first RDF peak yields components due to As-O and Fe-O correlations. As the As-O component at 1.67 A?? increases in size, the Fe-O component decreases, reflecting a decrease in Fe coordination about the average oxygen. This reduction is consistent with a decrease in mean crystallite size as suggested by EXAFS studies. Analysis of the second RDF peak components shows the progressive decrease in Fe-Fe correlations, and the enhancement of As-Fe correlations, as arsenate level increases. Comparison of the experimental RDF from coprecipitated arsenate-saturated FHY2 with simulated RDFs of model iron oxyhydroxyl structures further constrains possible sizes and geometry for the precipitates, and is consistent with sorbed complexes of the bidentate binuclear (apical oxygen sharing) type.

  15. Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi-Histidine Complexes of CuII, CuI and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

    PubMed Central

    Pushie, M. Jake; Nienaber, Kurt H.; McDonald, Alex; Millhauser, Glenn L.; George, Graham N.

    2014-01-01

    The metal coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of copper interaction with PrP just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, and yet the structural details of the various metal coordination modes have not been fully elucidated in some cases. Herein we employ X-ray absorption near edge spectroscopy as well as extended X-ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for CuII, CuI and ZnII with an N-terminal fragment of PrP. The PrP fragment constitutes four tandem repeats representative of the mammalian octarepeat domain, designated OR4, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations provide additional structural and thermodynamic data, and candidate structures are used to inform EXAFS data analysis. The optimized geometries from DFT calculations are used to identify potential coordination complexes for multi-histidine coordination of CuII, CuI and ZnII in an aqueous medium, modeled using 4-methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve fitting, using full multiple scattering on candidate structures from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of CuII, CuI and ZnII with the OR4 peptide at pH 7.4 at atomic resolution, which are best represented as a square planar [CuII(His)4]2+, digonal [CuI(His)2]+ and tetrahedral [ZnII(His)3(OH2)]2+, respectively. PMID:25042361

  16. Investigation of a Spin Transition in a LaCoO3 Single Crystal by the Method of X-Ray Magnetic Circular Dichroism at the Cobalt K- and L 2,3-Edges

    NASA Astrophysics Data System (ADS)

    Sikolenko, V. V.; Troyanchuk, I. O.; Karpinsky, D. V.; Rogalev, A.; Wilhelm, F.; Rosenberg, R.; Prabhakaran, D.; Efimova, E. A.; Efimov, V. V.; Tiutiunnikov, S. I.; Bobrikov, I. A.

    2018-02-01

    Spin transitions of cobalt ions in LaCoO3 single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L 2,3-edges of Co3+ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3 d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L 2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/ S from 0.48 to 0.53 in the temperature range from 60 K to 120 K.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  19. Total edge irregularity strength of (n,t)-kite graph

    NASA Astrophysics Data System (ADS)

    Winarsih, Tri; Indriati, Diari

    2018-04-01

    Let G(V, E) be a simple, connected, and undirected graph with vertex set V and edge set E. A total k-labeling is a map that carries vertices and edges of a graph G into a set of positive integer labels {1, 2, …, k}. An edge irregular total k-labeling λ :V(G)\\cup E(G)\\to \\{1,2,\\ldots,k\\} of a graph G is a labeling of vertices and edges of G in such a way that for any different edges e and f, weights wt(e) and wt(f) are distinct. The weight wt(e) of an edge e = xy is the sum of the labels of vertices x and y and the label of the edge e. The total edge irregularity strength of G, tes(G), is defined as the minimum k for which a graph G has an edge irregular total k-labeling. An (n, t)-kite graph consist of a cycle of length n with a t-edge path (the tail) attached to one vertex of a cycle. In this paper, we investigate the total edge irregularity strength of the (n, t)-kite graph, with n > 3 and t > 1. We obtain the total edge irregularity strength of the (n, t)-kite graph is tes((n, t)-kite) = \\lceil \\frac{n+t+2}{3}\\rceil .

  20. 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

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

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

    Shrestha, S; Vedantham, S; Karellas, A

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

  2. Local environment around gold (III) in aqueous chloride solutions: An EXAFS spectroscopy study

    NASA Astrophysics Data System (ADS)

    Farges, Franã§Ois; Sharps, Julia A.; Brown, Gordon E., Jr.

    1993-03-01

    The local environment around Au (III) in aqueous solutions containing 1 M NaCl was determined as a function of pH and Au concentration using X-ray absorption spectroscopy (XAS) at ambient temperature and pressure. The solution Au concentrations studied were 10 - to 10 -3 M and the pH ranged between 2 and 9.2. No significant changes of Au speciation were detected with increasing Au concentration; however, major speciation changes were caused by variations in pH. At pH = 2, Au is coordinated by four Cl atoms ( mean d [AuCl] = 2.28 -2.29 ± 0.01 Å), whereas at pH 7.5 and 9.2, Au is coordinated by three Cl and one O (or OH) and by two Cl and two O (or OH), respectively ( mean d[AuCl] = 2.28 ± 0.02 Å; mean d[AuO or AuOH] = 1.97 ± 0.02 Å), indicating replacement of Cl by O (or OH) with increasing pH. In all solutions studied, the number of first-neighbors around Au(III) is close to four. XANES analysis suggests the presence of a square-planar geometry for AuX 4 ( X = Cl, O) at all pH values studied. These results are in excellent agreement with those from our previous Raman, resonance Raman, and UV/visible spectroscopy study of gold(III)-chloride solutions (PECK et al., 1991), which found that AuCl 4-, AuCl 3(OH) -, and AuCl 2(OH) 2- are the majority species in the pH ranges 2-6, 6-8.5, and 8.5-11, respectively. We did not find evidence for Au(I)Cl 2- or Au(I)Cl(OH) - complexes in our pH 7.5 and 9.2 solutions, as was recently suggested by PAN and WOOD (1991) for acidic gold chloride solutions at temperatures > 100°C, although we can't rule these complexes out as minority species (<10% of the total Au in solution). Our EXAFS results also provide the first direct evidence for Cl second neighbors around AuCl 4- complexes in the most acidic solutions studied ( pH = 2 and 4.5). These second-neighbor Cl atoms were also detected at low Au concentrations (10 -3 M) and are similar in number and arrangement to those observed in crystalline KAuCL 4·2H 2O (two Cl

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

    USGS Publications Warehouse

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

    1999-01-01

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

  4. 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

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

    PubMed

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

    2008-10-16

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

  6. 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.

  7. The potential for neurovascular intravenous angiography using K-edge digital subtraction angiography

    NASA Astrophysics Data System (ADS)

    Schültke, E.; Fiedler, S.; Kelly, M.; Griebel, R.; Juurlink, B.; LeDuc, G.; Estève, F.; Le Bas, J.-F.; Renier, M.; Nemoz, C.; Meguro, K.

    2005-08-01

    Background: Catheterization of small-caliber blood vessels in the central nervous system can be extremely challenging. Alternatively, intravenous (i.v.) administration of contrast agent is minimally invasive and therefore carries a much lower risk for the patient. With conventional X-ray equipment, volumes of contrast agent that could be safely administered to the patient do not allow acquisition of high-quality images after i.v. injection, because the contrast bolus is extremely diluted by passage through the heart. However, synchrotron-based digital K-edge subtraction angiography does allow acquisition of high-quality images after i.v. administration of relatively small doses of contrast agent. Materials and methods: Eight adult male New Zealand rabbits were used for our experiments. Animals were submitted to both angiography with conventional X-ray equipment and synchrotron-based digital subtraction angiography. Results: With conventional X-ray equipment, no contrast was seen in either cerebral or spinal blood vessels after i.v. injection of iodinated contrast agent. However, using K-edge digital subtraction angiography, as little as 1 ml iodinated contrast agent, when administered as i.v. bolus, yielded images of small-caliber blood vessels in the central nervous system (both brain and spinal cord). Conclusions: If it would be possible to image blood vessels of the same diameter in the central nervous system of human patients, the synchrotron-based technique could yield high-quality images at a significantly lower risk for the patient than conventional X-ray imaging. Images could be acquired where catheterization of feeding blood vessels has proven impossible.

  8. An experimental study of a supercritical trailing-edge flow

    NASA Technical Reports Server (NTRS)

    Brown, J. L.; Viswanath, P. R.

    1984-01-01

    An experimental study has been conducted of a transonic, turbulent, high-Reynolds-number blunt trailing-edge flow. The model shape and the surface pressure distribution are characteristics of a modern supercritical airfoil under shock-free conditions. Reynolds number and pressure gradient scaling of the boundary layer are relevant to airfoil applications. The data set is exceptionally accurate and consistent, with the momentum balance accounting for the flux of momentum to within 1 percent, except in the immediate vicinity of the blunt trailing edge. The experimental flow exhibits strong viscous-inviscid interaction and higher-order boundary-layer effects including strong adverse streamwise pressure gradient, significant normal pressure gradients associated with surface and streamline curvature, and significant wake curvature. Navier-Stokes calculations with a two-equation K-epsilon turbulence model predict the correct pressure distribution which demonstrates the utility of these engineering tools. The experiment approaches separation at the strailing edge. However, in comparison to the experiment, the calculations predict too high skin friction and insufficient displacement thickness growth. An analysis of the turbulent and mean flow fields reveals the turbulence model defects are likely in modeling the dissipation source and sink terms, and in the eddy viscosity relation.

  9. XAFS studies of nickel and sulfur speciation in residual oil fly-ash particulate matters (ROFA PM).

    PubMed

    Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P; Linak, William P; Miller, C Andrew

    2007-02-15

    XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, depending upon the combustion conditions, lesser amounts of thiophenic sulfur, metal sulfide, and elemental sulfur may also be observed. Least-squares fitting of Ni K-edge XANES reveals that most of the nickel in PM is present as bioavailable NiSO4.nH2O. The insoluble Ni mainly exists as a minor species, as nickel ferrite in PM2.5 (PM < 2.5 microm) and nickel sulfide, Ni(x)SY(y) in PM2.5+ (PM > 2.5 microm). The Ni K-edge XANES results are in agreement with the EXAFS data. Such detailed speciation of Ni and S in PM is needed for determining their mobility, bioavailability, and reactivity, and hence, their role in PM toxicity. This information is also important for understanding the mechanism of PM formation, developing effective remediation measures, and providing criteria for identification of potential emission sources. Transition metals complexing with sulfur is ubiquitous in nature. Therefore, this information on metal sulfur complex can be critical to a large body of environmental literature.

  10. 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.

  11. 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.

  12. 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

  13. 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

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

    NASA Astrophysics Data System (ADS)

    Drury, Owen Byron

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

  15. A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

    PubMed Central

    Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

    2017-01-01

    Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

  16. EXAFS Study of Halato-Telechelic Polymers End-Capped With Group IVb Metal Carboxylates at Room and Low Temperatures

    NASA Astrophysics Data System (ADS)

    Vlaic, G.; Navarra, G.; Regnard, J.-R.; Williams, C. E.; Jérôme, R.

    1995-05-01

    The EXAFS analysis at 300, 70 and 5 K has shown that the thermal disorder is very low in a carboxylato telechelic polybutadiene neutralized with an increasing excess of Zr isopropoxide. Two types of Zr-O bonds in the first shell account for the experimental data. The Zr-O distances and number of oxygen neighbours in the two subshells are found to be independent of temperature in the investigated range. The proportion of Zr in the samples has no effect on the total number of oxygen atoms around Zr, in contrast to their relative distribution in the two subshells. The number of Zr atoms increases in the second shell with the total amount of this metal. Upon increasing degree of neutralization from 200 to 600%, the static disorder increases together with a strong reduction of the dynamic part of the Debye-Waller (DW) factor. At a high degree of neutralization (> 400%), the DW factor for the Zr-Zr bond is largely independent of temperature. These observations agree with formation of Zr polynuclear microdomains, the size and rigidity of which increase with the Zr content, in good agreement with the profound changes previously reported in the viscoelastic properties of these materials.

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

    NASA Astrophysics Data System (ADS)

    Piazza, F.

    2002-11-01

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

  18. LT-STM/STS studies of clean armchair edge

    NASA Astrophysics Data System (ADS)

    Ju, Zheng; Zhang, Wenhan; Wu, Weida; Weida Wu Team

    It was predicted and observed that the passivated zigzag edges of graphene host highly localized edge state. This edge state is predicted to be spin-polarized, which is appealing for spintronic applications. In contrast, no edge state was expected at passivated armchair graphene edge. Here we report low temperature scanning tunneling microscopy and spectroscopy (STM/STS) studies of electronic properties of clean monoatomic step edges on cleaved surface of HOPG. Most of step edges are armchair edges, in agreement with previous STM results. We observed only (√{ 3} ×√{ 3}) R30° superstructure near armchair edges, which has been reported in previous STM studies. On the other hand, no honeycomb superstructure was observed in our STM data. In addition, our STM results reveal an intriguing localized electronic state at clean armchair edges. Spectroscopic and spatial evolution of this edge state will be presented. This work is supported by NSF DMR-1506618.

  19. Bond compressibility and bond Grüneisen parameters of CdTe

    NASA Astrophysics Data System (ADS)

    Fornasini, P.; Grisenti, R.; Irifune, T.; Shinmei, T.; Mathon, O.; Pascarelli, S.; Rosa, A. D.

    2018-06-01

    Extended x-ray absorption fine structure (EXAFS) at the Cd K edge and diffraction patterns have been measured on CdTe as a function of pressure from 100 kPa (1 bar) to 5 GPa using a cell with nano-polycrystalline diamond anvils and an x-ray focussing scanning spectrometer. Three phases—zincblende (ZB), mixed cinnabar-ZB and rocksalt (RS)—are well distinguished in different pressure intervals. The bond compressibility measured by EXAFS in the ZB phase is slightly smaller than the one measured by diffraction and decreases significantly faster when the pressure increases; the difference is attributed to the effect of relative vibrations perpendicular to the Cd–Te bond. The parallel mean square relative displacement (MSRD) decreases, the perpendicular MSRD increases when the pressure increases, leading to an increasing anisotropy of relative atomic vibrations. A constant-temperature bond Grüneisen parameter (GP) has been evaluated for the ZB phase and compared with the constant-pressure bond GP measured in a previous experiment; an attempt is made to connect the bond GPs measured by EXAFS and the more familiar thermodynamic GP and mode GPs; the comparisons suggest the inadequacy of the quasi-harmonic approximation to deal with the local vibrational properties sampled by EXAFS.

  20. On the Total Edge Irregularity Strength of Generalized Butterfly Graph

    NASA Astrophysics Data System (ADS)

    Dwi Wahyuna, Hafidhyah; Indriati, Diari

    2018-04-01

    Let G(V, E) be a connected, simple, and undirected graph with vertex set V and edge set E. A total k-labeling is a map that carries vertices and edges of a graph G into a set of positive integer labels {1, 2, …, k}. An edge irregular total k-labeling λ: V(G) ∪ E(G) → {1, 2, …, k} of a graph G is a total k-labeling such that the weights calculated for all edges are distinct. The weight of an edge uv in G, denoted by wt(uv), is defined as the sum of the label of u, the label of v, and the label of uv. The total edge irregularity strength of G, denoted by tes(G), is the minimum value of the largest label k over all such edge irregular total k-labelings. A generalized butterfly graph, BFn , obtained by inserting vertices to every wing with assumption that sum of inserting vertices to every wing are same then it has 2n + 1 vertices and 4n ‑ 2 edges. In this paper, we investigate the total edge irregularity strength of generalized butterfly graph, BFn , for n > 2. The result is tes(B{F}n)=\\lceil \\frac{4n}{3}\\rceil .

  1. In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

    PubMed

    Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta

    2015-11-01

    Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

  2. Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

    PubMed

    Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

    2005-07-19

    Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

  3. 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.

  4. Cell edge detection in JPEG2000 wavelet domain - analysis on sigmoid function edge model.

    PubMed

    Punys, Vytenis; Maknickas, Ramunas

    2011-01-01

    Big virtual microscopy images (80K x 60K pixels and larger) are usually stored using the JPEG2000 image compression scheme. Diagnostic quantification, based on image analysis, might be faster if performed on compressed data (approx. 20 times less the original amount), representing the coefficients of the wavelet transform. The analysis of possible edge detection without reverse wavelet transform is presented in the paper. Two edge detection methods, suitable for JPEG2000 bi-orthogonal wavelets, are proposed. The methods are adjusted according calculated parameters of sigmoid edge model. The results of model analysis indicate more suitable method for given bi-orthogonal wavelet.

  5. 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.

  6. 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

  7. Simulation design of high reverse blocking high-K/low-K compound passivation AlGaN/GaN Schottky barrier diode with gated edge termination

    NASA Astrophysics Data System (ADS)

    Bai, Zhiyuan; Du, Jiangfeng; Xin, Qi; Li, Ruonan; Yu, Qi

    2017-11-01

    In this paper, a novel high-K/low-K compound passivation AlGaN/GaN Schottky Barrier Diode (CPG-SBD) is proposed to improve the off-state characteristics of AlGaN/GaN schottky barrier diode with gated edge termination (GET-SBD) by adding low-K blocks in to the high-K passivation layer. The reverse leakage current of CPG-SBD can be reduced to 1.6 nA/mm by reducing the thickness of high-K dielectric under GET region to 5 nm, while the forward voltage and on-state resistance keep 1 V and 3.8 Ω mm, respectively. Breakdown voltage of CPG-SBDs can be improved by inducing discontinuity of the electric field at the high-K/low-K interface. The breakdown voltage of the optimized CPG-SBD with 4 blocks of low-K can reach 1084 V with anode to cathode distance of 5 μm yielding a high FOM of 5.9 GW/cm2. From the C-V simulation results, CPG-SBDs induce no parasitic capacitance by comparison of the GET-SBDs.

  8. 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.

  9. 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.

  10. Minimizing the Diameter of a Network Using Shortcut Edges

    NASA Astrophysics Data System (ADS)

    Demaine, Erik D.; Zadimoghaddam, Morteza

    We study the problem of minimizing the diameter of a graph by adding k shortcut edges, for speeding up communication in an existing network design. We develop constant-factor approximation algorithms for different variations of this problem. We also show how to improve the approximation ratios using resource augmentation to allow more than k shortcut edges. We observe a close relation between the single-source version of the problem, where we want to minimize the largest distance from a given source vertex, and the well-known k-median problem. First we show that our constant-factor approximation algorithms for the general case solve the single-source problem within a constant factor. Then, using a linear-programming formulation for the single-source version, we find a (1 + ɛ)-approximation using O(klogn) shortcut edges. To show the tightness of our result, we prove that any ({3 over 2}-ɛ)-approximation for the single-source version must use Ω(klogn) shortcut edges assuming P ≠ NP.

  11. Theory of K-edge resonant inelastic x-ray scattering and its application for La0.5Sr1.5MnO4

    NASA Astrophysics Data System (ADS)

    Seman, T. F.; Liu, X.; Hill, J. P.; van Veenendaal, M.; Ahn, K. H.

    2013-03-01

    We present a formula based on tight-binding approach for the calculation of K-edge resonant inelastic x-ray scattering spectrum for transition metal oxides, by extending the previous result [K. H. Ahn, A. J. Fedro, and M. van Veenendaal, Phys. Rev. B 79, 045103 (2009).] to include explicit momentum dependence and a basis with multiple core hole sites. We apply this formula to layered charge, orbital, and spin ordered manganites, La0.5Sr1.5MnO4. The K-edge RIXS spectrum is found not periodic with respect to the actual reciprocal lattice, but approximately periodic with respect to the reciprocal lattice for the hypothetical unit cell with one core hole site. With experimental strcuture and reasonable tight-binding parameters, we obtain good agreement with experimental data, in particular, with regards to the large variation of the intensity with momentum. We find that the screening in La0.5Sr1.5MnO4 is highly localized around the core hole site and demonstrate the potential of K-edge RIXS as a probe for the screening dynamics in materials. Work supported by US.DOE Contr. DE-AC02-98CH10886 (X.L.,J.H.), US.DOE Award DE-FG02-03ER46097 (M.v.V.), CMCSN under Grants DE-FG02-08ER46540 & DE-SC0007091 (T.S.,K.A.,M.v.V.), Argonne XSD Visitor Prog.(K.A.), US.DOE Contr. DE-AC02-06CH11357 (X.L.,J.H).

  12. Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

    PubMed

    Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

    2009-05-01

    The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

  13. Optimization of the K-edge imaging for vulnerable plaques using gold nanoparticles and energy-resolved photon counting detectors: a simulation study

    PubMed Central

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q.; Ducote, Justin; Molloi, Sabee

    2014-01-01

    We investigated the effect of different imaging parameters such as dose, beam energy, energy resolution, and number of energy bins on image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. Maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of plaque's inflammation. The simulations studies used a single slice parallel beam CT geometry with an X-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33x24 cm2) phantom, where both phantoms contained tissue, calcium, and gold. In the simulation studies GNP quantification and background (calcium and tissue) suppression task were pursued. The X-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% FWHM energy resolution) implementations of photon counting detector were simulated. The simulations were performed for the CdZnTe detector with pixel pitch of 0.5-1 mm, which corresponds to the performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the X-ray beam energy (kVp) to achieve the highest signal-to-noise ratio (SNR) with respect to patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at 125 kVp X-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 μmol/mL (0.21 mg/mL) for an ideal detector and about 2.5 μmol/mL (0.49 mg/mL) for more realistic (12% FWHM) detector. The studies show the optimal imaging parameters at lowest patient dose using an energy resolved photon counting detector

  14. 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

  15. 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.

  16. 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.

  17. Optimization of K-edge imaging for vulnerable plaques using gold nanoparticles and energy resolved photon counting detectors: a simulation study.

    PubMed

    Alivov, Yahya; Baturin, Pavlo; Le, Huy Q; Ducote, Justin; Molloi, Sabee

    2014-01-06

    We investigated the effect of different imaging parameters, such as dose, beam energy, energy resolution and the number of energy bins, on the image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. A maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of the plaque's inflammation. The simulation studies used a single-slice parallel beam CT geometry with an x-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33 × 24 cm(2)) phantoms, where both phantoms contained tissue, calcium and gold. In the simulation studies, GNP quantification and background (calcium and tissue) suppression tasks were pursued. The x-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% full width at half maximum (FWHM) energy resolution) implementations of the photon counting detector were simulated. The simulations were performed for the CdZnTe detector with a pixel pitch of 0.5-1 mm, which corresponds to a performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the x-ray beam energy (kVp) to achieve the highest signal-to-noise ratio with respect to the patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at the 125 kVp x-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 µmol mL(-1) (0.21 mg mL(-1)) for an ideal detector and about 2.5 µmol mL(-1) (0.49 mg mL(-1)) for a more realistic (12% FWHM) detector. The studies show the optimal

  18. 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.

  19. K-edge Subtraction Angiography with Synchrotron X-Rays: Final Technical Report, (February 1, 1984 to January 31, 1987)

    DOE R&D Accomplishments Database

    Hofstadter, R.

    1987-09-01

    The aim was the development of an angiographic method and appropriate equipment for imaging with x-rays the coronary arteries in a non-invasive manner. Successive steps involved studies with phantoms, live animals and finally with human subjects. Clinical evaluation of human coronary arteries remains a goal of this and a continuing project, and steps along the way to such an achievement are in process. Transvenous injection of a dye using the method of iodine dichromography near 33.2 keV, the K-edge of iodine, forms the basis of the method

  20. 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

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  3. EXAFS spectrum peculiarities of Y 1- xYb xNi 2B 2C

    NASA Astrophysics Data System (ADS)

    Cortes, R.; Fomicheva, L. N.; Menushenkov, A. P.; Meyer-Klaucke, W.; Konarev, P. V.; Tsvyashchenko, A. V.

    2001-09-01

    The results on the temperature dependent EXAFS studies of the local structure peculiarities of Y 1- xYb xNi 2B 2C series synthesized at a high pressure of 8 GPa are presented. The interrelation between the local structure of Y 1- xYb xNi 2B 2C and its superconducting and magnetic properties was observed supporting the model where the contributions from all type of the nearest atoms to the electron-phonon coupling are important and cannot be neglected.

  4. Demonstration of iodine K-edge imaging by use of an energy-discrimination X-ray computed tomography system with a cadmium telluride detector.

    PubMed

    Abudurexiti, Abulajiang; Kameda, Masashi; Sato, Eiichi; Abderyim, Purkhet; Enomoto, Toshiyuki; Watanabe, Manabu; Hitomi, Keitaro; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Takahashi, Kiyomi; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

    2010-07-01

    An energy-discrimination K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region by utilizing contrast media. The CT system has a cadmium telluride (CdTe) detector, and a projection curve is obtained by linear scanning with use of the CdTe detector in conjunction with an X-stage. An object is rotated by a rotation step angle with use of a turntable between the linear scans. Thus, CT is carried out by repetition of the linear scanning and the rotation of an object. Penetrating X-ray photons from the object are detected by the CdTe detector, and event signals of X-ray photons are produced with use of charge-sensitive and shaping amplifiers. Both the photon energy and the energy width are selected by use of a multi-channel analyzer, and the number of photons is counted by a counter card. For performing energy discrimination, a low-dose-rate X-ray generator for photon counting was developed; the maximum tube voltage and the minimum tube current were 110 kV and 1.0 microA, respectively. In energy-discrimination CT, the tube voltage and the current were 60 kV and 20.0 microA, respectively, and the X-ray intensity was 0.735 microGy/s at 1.0 m from the source and with a tube voltage of 60 kV. Demonstration of enhanced iodine K-edge X-ray CT was carried out by selection of photons with energies just beyond the iodine K-edge energy of 33.2 keV.

  5. 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.

  6. Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

    Darab, J.G.; Linehan, J.C.; Matson, D.W.

    1993-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

  7. Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

    Darab, J.G.; Linehan, J.C.; Matson, D.W.

    1993-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

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

    PubMed

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

    2016-03-01

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

  9. DAVs: Red Edge and Outbursts

    NASA Astrophysics Data System (ADS)

    Luan, Jing

    2018-04-01

    As established by ground based surveys, white dwarfs with hydrogen atmospheres pulsate as they cool across the temperature range, 12500K< Teff < 10800K . Known as DAVs or ZZ Ceti stars, their oscillations are attributed to overstable g-modes excited by convective driving. The effective temperature at the blue edge of the instability strip is slightly lower than that at which a surface convection zone appears. The temperature at the red edge is a two-decade old puzzle. Recently, Kepler discovered a number of cool DAVs exhibiting sporadic outbursts separated by days, each lasting several hours, and releasing \\sim 10^{33}-10^{34} {erg}. We provide quantitative explanations for both the red edge and the outbursts. The minimal frequency for overstable modes rises abruptly near the red edge. Although high frequency overstable modes exist below the red edge, their photometric amplitudes are generally too small to be detected by ground based observations. Nevertheless, these overstable parent modes can manifest themselves through nonlinear mode couplings to damped daughter modes which generate limit cycles giving rise to photometric outbursts.

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

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

    Siqueira, M. C.; Maia, R. N. A.; Araujo, R. M. T.

    In this article, we investigated structural and thermal properties of an amorphous alloy of the Ga–Se system. The amorphous GaSe{sub 9} alloy was produced by mechanical alloying and it was studied using EXAFS spectroscopy and cumulant expansion method. We also made reverse Monte Carlo simulations using the total structure factor S(K) obtained from x-ray diffraction and the EXAFS χ(k) oscillations on Se and Ga K edges as input data. Several parameters, such as average coordination numbers and interatomic distances, structural and thermal disorders, asymmetry of the partial distribution functions g{sub ij}(r), and Einstein and Debye temperatures, were determined. The g{submore » ij}{sup E}(r) functions were reconstructed from the cumulants C{sub 1}, C{sub 2}, and C{sub 3} obtained from the Einstein model, and they were compared to the g{sub ij}{sup RMC}(r) functions obtained from the simulations. The simulations also furnished the partial bond angle distribution functions Θ{sub ijℓ}(cosθ), which describe the angular distribution of bonds between first neighbors, and give information about the kind of structural units present in the alloy.« less

  12. Study on Trailing Edge Ramp of Supercritical Airfoil

    DTIC Science & Technology

    2016-03-30

    7 th Asia-Pacific International Symposium on Aerospace Technology, 25 – 27 November 2015, Cairns Study on Trailing Edge Ramp of Supercritical...China Abstract Trailing edge flow control method could improve the performance of supercritical airfoil with a small modification on the original...airfoil. In this paper, a ramp of 2%~7% chord length is sliced near the trailing edge to improve airfoil performance. The trailing edge ramp is

  13. Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

    PubMed

    Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

    2011-09-15

    Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

  14. Self-irradiation damage to the local structure of plutonium and plutonium intermetallics

    NASA Astrophysics Data System (ADS)

    Booth, C. H.; Jiang, Yu; Medling, S. A.; Wang, D. L.; Costello, A. L.; Schwartz, D. S.; Mitchell, J. N.; Tobash, P. H.; Bauer, E. D.; McCall, S. K.; Wall, M. A.; Allen, P. G.

    2013-03-01

    The effect of self-irradiation damage on the local structure of δ-Pu, PuAl2, PuGa3, and other Pu intermetallics has been determined for samples stored at room temperature using the extended x-ray absorption fine-structure (EXAFS) technique. These measurements indicate that the intermetallic samples damage at a similar rate as indicated in previous studies of PuCoGa5. In contrast, δ-Pu data indicate a much slower damage accumulation rate. To explore the effect of storage temperature and possible room temperature annealing effects, we also collected EXAFS data on a δ-Pu sample that was held at less than 32 K for a two month period. This sample damaged much more quickly. In addition, the measurable damage was annealed out at above only 135 K. Data from samples of δ-Pu with different Ga concentrations and results on all samples collected from different absorption edges are also reported. These results are discussed in terms of the vibrational properties of the materials and the role of Ga in δ-Pu as a network former.

  15. Roman coloured and opaque glass: a chemical and spectroscopic study

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  19. Practical Study for the Properties of Hueckel Edge Detection Operator

    NASA Astrophysics Data System (ADS)

    Jabbar, Hameed M. Abdul; Hatem, Amal J.; Ameer, Inbethaq M. A. Abdul

    2018-05-01

    The first practical study for the Hueckel edge detection operator was presented in this research, where it is tested on standard step edge set images. A number of criteria were adopted to evaluate its practical performance, which is the accuracy in detecting the edges direction, the error in the edges location (dislocation), edges width, the calculated edge goodness criterion and the consumed execution time. These criteria were studied with the edge direction and the used disk radius of the Hueckel edge detection operator. Important notes were recorded for the performance of this operator depending on the direction of the edge and/or with the radius of the used disk. There is a variation in the performance of the operator in terms of precision in detecting of the edges direction and position. A discussion was presented for the all criteria adopted in the research.

  20. 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.

  1. Magnetism of Nanographene-Based Microporous Carbon and Its Applications: Interplay of Edge Geometry and Chemistry Details in the Edge State

    NASA Astrophysics Data System (ADS)

    Enoki, Toshiaki; Kiguchi, Manabu

    2018-03-01

    This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. Nanographenes have important edge geometry dependence in their electronic structures. In armchair edges, electron wave interference works to contribute to energetic stability. Meanwhile, zigzag edges possess an edge-localized and spin-polarized nonbonding edge state, which causes electronic, magnetic, and chemical activities. In addition to the geometry dependence, the electronic structures are seriously affected by edge chemistry details. The edge chemistry dependence together with edge geometries on the electronic structures are discussed with samples of randomly networked nanographenes (microporous activated carbon fibers) in pristine state and under high-temperature annealing. In the pristine sample with the edges oxidized in ambient atmospheric conditions, the edge state, which is otherwise unstable, can be stabilized because of the charge transfer from nanographene to terminating oxygen. Nanographene, whose edges consist of a combination of magnetic zigzag edges and nonmagnetic armchair edges, is found to be ferrimagnetic with a nonzero net magnetic moment created under the interplay between a strong intrazigzag-edge ferromagnetic interaction and intermediate-strength interzigzag-edge antiferromagnetic-ferromagnetic interaction. At heat-treatment temperatures just below the fusion start (approximately 1500 K), the edge-terminating structure is changed from oxygen-containing groups to hydrogen in the nanographene network. Additionally, hydrogen-terminated zigzag edges, which are present as the majority and chemically unstable, play a triggering role in fusion above 1500 K. The fusion start brings about an insulator-to-metal transition at TI -M˜1500 K . Local fusions taking place percolatively between nanographenes work to expand the π -bond network, eventually resulting in the development of antiferromagnetic short-range order toward spin glass in the

  2. Hydrous ferric oxide: evaluation of Cd-HFO surface complexation models combining Cd(K) EXAFS data, potentiometric titration results, and surface site structures identified from mineralogical knowledge.

    PubMed

    Spadini, Lorenzo; Schindler, Paul W; Charlet, Laurent; Manceau, Alain; Vala Ragnarsdottir, K

    2003-10-01

    The surface properties of ferrihydrite were studied by combining wet chemical data, Cd(K) EXAFS data, and a surface structure and protonation model of the ferrihydrite surface. Acid-base titration experiments and Cd(II)-ferrihydrite sorption experiments were performed within 3<-log[H(+)]<10.5 and 0.5<[Cd(t)]<12 mM in 0.3 M NaClO(4) at 25 degrees C, where [Cd(t)] refers to total Cd concentration. Measurements at -5.5triple bond Fe-OH(-1/2),logk((int))=-8.29, assuming the existence of a unique intrinsic microscopic constant, logk((int)), and consequently the existence of a single significant type of acid-base reactive functional groups. The surface structure model indicates that these groups are terminal water groups. The Cd(II) data were modeled assuming the existence of a single reactive site. The model fits the data set at low Cd(II) concentration and up to 50% surface coverage. At high coverage more Cd(II) ions than predicted are adsorbed, which is indicative of the existence of a second type of site of lower affinity. This agrees with the surface structure and protonation model developed, which indicates comparable concentrations of high- and low-affinity sites. The model further shows that for each class of low- and high-affinity sites there exists a variety of corresponding Cd surface complex structure, depending on the model crystal faces on which the complexes develop. Generally, high-affinity surface structures have surface coordinations of 3 and 4, as compared to 1 and 2 for low-affinity surface structures.

  3. Three dimensional mapping of strontium in bone by dual energy K-edge subtraction imaging

    NASA Astrophysics Data System (ADS)

    Cooper, D. M. L.; Chapman, L. D.; Carter, Y.; Wu, Y.; Panahifar, A.; Britz, H. M.; Bewer, B.; Zhouping, W.; Duke, M. J. M.; Doschak, M.

    2012-09-01

    The bones of many terrestrial vertebrates, including humans, are continually altered through an internal process of turnover known as remodeling. This process plays a central role in bone adaptation and disease. The uptake of fluorescent tetracyclines within bone mineral is widely exploited as a means of tracking new tissue formation. While investigation of bone microarchitecture has undergone a dimensional shift from 2D to 3D in recent years, we lack a 3D equivalent to fluorescent labeling. In the current study we demonstrate the ability of synchrotron radiation dual energy K-edge subtraction (KES) imaging to map the 3D distribution of elemental strontium within rat vertebral samples. This approach has great potential for ex vivo analysis of preclinical models and human tissue samples. KES also represents a powerful tool for investigating the pharmokinetics of strontium-based drugs recently approved in many countries around the globe for the treatment of osteoporosis.

  4. Numerical study of delta wing leading edge blowing

    NASA Technical Reports Server (NTRS)

    Yeh, David; Tavella, Domingo; Roberts, Leonard

    1988-01-01

    Spanwise and tangential leading edge blowing as a means of controlling the position and strength of the leading edge vortices are studied by numerical solution of the three-dimensional Navier-Stokes equations. The leading edge jet is simulated by defining a permeable boundary, corresponding to the jet slot, where suitable boundary conditions are implemented. Numerical results are shown to compare favorably with experimental measurements. It is found that the use of spanwise leading edge blowing at moderate angle of attack magnifies the size and strength of the leading edge vortices, and moves the vortex cores outboard and upward. The increase in lift primarily comes from the greater nonlinear vortex lift. However, spanwise blowing causes earlier vortex breakdown, thus decreasing the stall angle. The effects of tangential blowing at low to moderate angles of attack tend to reduce the pressure peaks associated with leading edge vortices and to increase the suction peak around the leading edge, so that the integrated value of the surface pressure remains about the same. Tangential leading edge blowing in post-stall conditions is shown to re-establish vortical flow and delay vortex bursting, thus increasing C sub L sub max and stall angle.

  5. Soft X-ray spectromicroscopy study of mineral-organic matter associations in pasture soil clay fractions.

    PubMed

    Chen, Chunmei; Dynes, James J; Wang, Jian; Karunakaran, Chithra; Sparks, Donald L

    2014-06-17

    There is a growing acceptance that associations with soil minerals may be the most important overarching stabilization mechanism for soil organic matter. However, direct investigation of organo-mineral associations has been hampered by a lack of methods that can simultaneously characterize organic matter (OM) and soil minerals. In this study, STXM-NEXAFS spectroscopy at the C 1s, Ca 2p, Fe 2p, Al 1s, and Si 1s edges was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope. Bulk techniques including C and N NEXAFS, Fe K-edge EXAFS spectroscopy, and XRD were applied to provide additional information. Results demonstrated that C was associated with Ca, Fe, Al, and Si with no separate phase in soil clay particles. In soil clay particles, the pervasive C forms were aromatic C, carboxyl C, and polysaccharides with the relative abundance of carboxyl C and polysaccharides varying spatially at the submicrometer scale. Only limited regions in the soil clay particles had aliphatic C. Good C-Ca spatial correlations were found for soil clay particles with no CaCO3, suggesting a strong role of Ca in organo-mineral assemblage formation. Fe EXAFS showed that about 50% of the total Fe in soils was contained in Fe oxides, whereas Fe-bearing aluminosilicates (vermiculite and Illite) accounted for another 50%. Fe oxides in the soil were mainly crystalline goethite and hematite, with lesser amounts of poorly crystalline ferrihydrite. XRD revealed that soil clay aluminosilicates were hydroxy-interlayered vermiculite, Illite, and kaolinite. C showed similar correlation with Fe to Al and Si, implying a similar association of Fe oxides and aluminosilicates with organic matter in organo-mineral associations. These direct microscopic determinations can help improve understanding of organo-mineral interactions in soils.

  6. Oxygen K- and Mn L-Edges of La_xMn_yO_3-d Films

    NASA Astrophysics Data System (ADS)

    Deleon, Michael; Tyson, Trevor; Qian, Q.; Dubourdieu, C.; Senateur, J. P.; Bosak, A.; Arena, D. A.

    2003-03-01

    The La_xMn_yO_3-d system holds much interest due to it's wide range of magnetic and transport properties with varying compositions. Oxygen defects and lanthanum deficiencies in the parent compound LaMnO3 induce a mixture of valences at the Mn site which enables transitions to a ferromagnetic metallic state through double exchange [1-5]. We have measured the oxygen K-edges and Mn L-edges for La_xMn_yO_3-d films of varying x deposited on (100) SrTiO3 and x=0.8 on varying thickness deposited on (001) LaAlO_3. These results are interpreted by multiplet structure computations. In addition, band structure results will be used to track changes in unoccupied levels on the Mn and O sites. This work is supported by NSF Career Grant DMR-9733862 and DMR-0209243. [1]A. Gupta, T.R. McGuire, P.R. Duncombe, M. Rupp, J. Z. Sun, W. J. Gallagher, G. Xiao. Appl. Phys. Let. 67, 3494 (1995) [2]P. S. I. P. N. de Silva, F.M. Richards, L. F. Cohen, J. A. Alonso, M. J. Martinez-Lope, M. T. Casais, K. A. Thomas, J. L. MacManus-Driscoll. J. A. Phys. 83, 3394(1998) [3] C. Chen, A. de Lozanne. A. Phys. Let. 73, 3950(1998) [4] S. J. Kim, C. S. Kim, S. Park, B. W. Lee. J. A. Phys. 89, 7416 (2001) [5] J. Topfer, J. B. Goodenough. Sol. St. Ionics 101, 1215 (1997)

  7. 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.

  8. Characterization by 27Al NMR, X-ray absorption spectroscopy, and density functional theory techniques of the species responsible for benzene hydrogenation in Y zeolite-supported carburized molybdenum catalysts.

    PubMed

    Rocha, Angela S; da Silva, Victor Teixeira; Eon, Jean G; de Menezes, Sônia M C; Faro, Arnaldo C; Rocha, Alexandre B

    2006-08-17

    Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.

  9. On Super Edge-magic Total Labeling of Modified Watermill Graph

    NASA Astrophysics Data System (ADS)

    Nurdin; Ungko, T. S.; Gormantara, J.; Abdullah, A.; Aulyah, S.; Nikita

    2018-03-01

    An edge-magic total labeling on a graph G is one-to-one map from V(G) ∪ E(G) onto the set of integers 1,2, ...,ν + e, where ν = |V(G)| and e = |E(G)|, with the property that, given any edge uv, f(u) + f(u, ν}) + f(ν) = k for every u,v ∈ V(G), and k is called magic valuation. An edge-magic total labeling f is called super edge-magic total if f(v(G)) = {1,2 ...,|V(G)|} and f(E(G)) = {|V(G)| + 1, |V(G)| + 2,... |V(G) + E(G)|}. In this paper we investigate edge-magic total labeling of a new graph called modified Watermill graph. Furthermore, the magic valuation of the modified Watermill graph WM(n) is k=\\frac{1}{2}(21n+3), for n odd, n ≥ 3.

  10. 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

  11. Numerical studies of edge localized instabilities in tokamaks

    NASA Astrophysics Data System (ADS)

    Wilson, H. R.; Snyder, P. B.; Huysmans, G. T. A.; Miller, R. L.

    2002-04-01

    A new computational tool, edge localized instabilities in tokamaks equilibria (ELITE), has been developed to help our understanding of short wavelength instabilities close to the edge of tokamak plasmas. Such instabilities may be responsible for the edge localized modes observed in high confinement H-mode regimes, which are a serious concern for next step tokamaks because of the high transient power loads which they can impose on divertor target plates. ELITE uses physical insight gained from analytic studies of peeling and ballooning modes to provide an efficient way of calculating the edge ideal magnetohydrodynamic stability properties of tokamaks. This paper describes the theoretical formalism which forms the basis for the code.

  12. Resonant Soft X-ray Scattering studies with Transition Edge Sensors

    NASA Astrophysics Data System (ADS)

    Fang, Yizhi; Lee, Sangjun; de La Pena, Gilberto; Sun, Xiaolan; Rodolakis, Fanny; McChesney, Jessica; Fowler, Joe; Joe, Young Il; Doriese, William; Morgan, Kelsey; Swetz, Daniel; Ullom, Joel; Abbamonte, Peter

    Resonant Soft X-ray has been one of the key techniques to study charge orders in high Tc cuperates. To solve the issue of unwanted enhancement of inelastic florescence background at resonance, we have developed an energy-resolving superconducting Transition-Edge Sensor microcalorimeters. These superconducting sensors obtain exquisite energy resolution by exploiting the superconducting-to-normal transition to photon energy and by operating at cryogenic temperatures ( 70 mK) where thermal noise is minimal. This TES has demonstrated 1.0 eV resolution below 1 keV. We present first results using this detector to study the (002) Bragg peak and specular elastic scattering from a single crystal of stripe-ordered La 2 - x Bax CuO4 (x=0.125). Use of this detector for studying excitations and rejecting background fluorescence will be discussed.

  13. A comprehensive study on pavement edge line implementation.

    DOT National Transportation Integrated Search

    2014-04-01

    The previous 2011 study Safety Improvement from Edge Lines on Rural Two-Lane Highways analyzed the crash data of : three years before and one year after edge line implementation by using the latest safety analysis statistical method. It : concl...

  14. Planar Lattice Instability in LA2CUO4.1 across the Superconducting Transition

    NASA Astrophysics Data System (ADS)

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

    2001-03-01

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

  15. Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

    USGS Publications Warehouse

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

    2004-01-01

    The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and <45 ??m size fractions (e.g., from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases

  16. High-performance thermoelectricity in edge-over-edge zinc-porphyrin molecular wires.

    PubMed

    Noori, Mohammed; Sadeghi, Hatef; Lambert, Colin J

    2017-04-20

    If high efficiency organic thermoelectric materials could be identified, then these would open the way to a range of energy harvesting technologies and Peltier coolers using flexible and transparent thin-film materials. We have compared the thermoelectric properties of three zinc porphyrin (ZnP) dimers and a ZnP monomer and found that the "edge-over-edge" dimer formed from stacked ZnP rings possesses a high electrical conductance, negligible phonon thermal conductance and a high Seebeck coefficient of the order of 300 μV K -1 . These combine to yield a predicted room-temperature figure of merit of ZT ≈ 4, which is the highest room-temperature ZT ever reported for a single organic molecule. This high value of ZT is a consequence of the low phonon thermal conductance arising from the stacked nature of the porphyrin rings, which hinders phonon transport through the edge-over-edge molecule and enhances the Seebeck coefficient.

  17. Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

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

    Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

    The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption nearmore » edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the

  18. Quantifying edge significance on maintaining global connectivity

    PubMed Central

    Qian, Yuhua; Li, Yebin; Zhang, Min; Ma, Guoshuai; Lu, Furong

    2017-01-01

    Global connectivity is a quite important issue for networks. The failures of some key edges may lead to breakdown of the whole system. How to find them will provide a better understanding on system robustness. Based on topological information, we propose an approach named LE (link entropy) to quantify the edge significance on maintaining global connectivity. Then we compare the LE with the other six acknowledged indices on the edge significance: the edge betweenness centrality, degree product, bridgeness, diffusion importance, topological overlap and k-path edge centrality. Experimental results show that the LE approach outperforms in quantifying edge significance on maintaining global connectivity. PMID:28349923

  19. A Comparative XAFS Study of Gold-thiolate Nanoparticles and Nanoclusters

    NASA Astrophysics Data System (ADS)

    Chevrier, D. M.; Chatt, A.; Sham, T. K.; Zhang, P.

    2013-04-01

    Tiopronin-capped gold nanoparticles and gold nanoclusters of sizes 3.0 and 1.5 nm, respectively, were investigated with XAFS at the gold L3-edge. The specific EXAFS fitting procedure is discussed for obtaining reliable fit parameters for each system. The difficulties and challenges faced when analysing EXAFS data for gold nanoparticles and nanoclusters are also mentioned. Fitting results for gold nanoparticles reveal a small amount of surface Au-thiolate interactions with a large Au-Au metal core. For gold nanoclusters, only a one-shell fit was obtainable. Instead of Au-Au metal core, long-range interactions are expected for gold nanoclusters. Tiopronin-capped gold nanoclusters are proposed to be polymeric in nature, which helps explain the observed red luminescence.

  20. Comprehensive studies of structural, electronic and magnetic properties of Zn{sub 0.95}Co{sub 0.05}O nanopowders

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

    Radisavljević, Ivana, E-mail: iva@vin.bg.ac.rs; Novaković, Nikola; Matović, Branko

    2016-02-15

    Highlights: • Zn{sub 0.95}Co{sub 0.05}O nanopowders are characterized by high structural order. • Co atoms show no tendency for Co–Co clustering and Co–Ov complexes formation. • Co–O–Co clustering along the c-axis has not lead to ferromagnetic order. • XMCD provides no evidence of magnetic polarization of O 2p and Co 3d states. - Abstract: X-ray absorption (XANES, EXAFS, XMCD) and photoelectron (XPS) spectroscopic techniques were employed to study local structural, electronic and magnetic properties of Zn{sub 0.95}Co{sub 0.05}O nanopowders. The substitutional Co{sup 2+} ions are incorporated in ZnO lattice at regular Zn sites and the sample is characterized by highmore » structural order. There was no sign of ferromagnetic ordering of Co magnetic moments and the sample is in paramagnetic state at all temperatures down to 5 K. The possible connection of the structural defects with the absence of ferromagnetism is discussed on the basis of theoretical calculations of the O K-edge absorption spectra.« less

  1. Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

    PubMed

    Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

    2013-02-13

    Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  2. Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

    PubMed

    Nie, Zhe; Finck, Nicolas; Heberling, Frank; Pruessmann, Tim; Liu, Chunli; Lützenkirchen, Johannes

    2017-04-04

    Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

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

    PubMed

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

    2017-02-06

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

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

    DOE PAGES

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

    2017-01-09

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

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

    USGS Publications Warehouse

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

    2000-01-01

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

  6. XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

    PubMed

    Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

    2018-06-01

    Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Resonant inelastic X-ray scattering spectrometer with 25meV resolution at the Cu K -edge

    DOE PAGES

    Ketenoglu, Didem; Harder, Manuel; Klementiev, Konstantin; ...

    2015-06-27

    An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the CuK-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO 2) pixels, the spectrometer delivers a resolution near 25meV (FWHM) at 8981eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick–Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

  8. Initial Edge Stability Observations in the PEGASUS Toroidal Experiment

    NASA Astrophysics Data System (ADS)

    Bongard, M. W.; Battaglia, D. J.; Garstka, G. D.; Sontag, A. C.; Unterberg, E. A.

    2007-11-01

    Edge stability is an important consideration for design of fusion experiments, as transient heat loads generated by edge instabilities may damage the first wall. Such instabilities are now believed to include peeling (current driven) and ballooning (pressure driven) components. Peeling instability may be expected for high values of edge j||/B and low edge pressure gradient. This matches the operating space of Pegasus, with typical ˜100 kA/m^2, |B|˜ 0.01 T, and an L-mode edge. A new camera system has observed filamentary structures in the edge of nearly all ohmically-heated discharges. Ideal stability analysis of these discharges with DCON indicates marginal stability to resistive interchange for ψN>= 0.95. Modification of triangularity during startup is observed to delay instability onset. A plasma control system based on that used on DIII-D will allow study of the influence of plasma shaping on mode stability characteristics. An array of magnetic probes capable of insertion into the scrape-off layer and plasma edge is being developed to provide a local constraint on the edge current profile.

  9. Photoionization of Ne Atoms and Ne + Ions Near the K Edge: PrecisionSpectroscopy and Absolute Cross-sections

    DOE PAGES

    Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander; ...

    2017-02-17

    Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s 2p 6 2S 1/2) level, for example, requires cooperative interaction of at least four electrons.« less

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

    PubMed

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

    2009-09-10

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

  11. Metal oxidation states in biological water splitting† †Electronic supplementary information (ESI) available: Additional methodological details and discussion, Tables S1–S10, Fig. S1–S16, spin populations, parameters of optimized structures, experimental details and analysis of 55Mn ENDOR at 2.5 K, analysis of calculated Mn K pre-edge XAS, discussion of reduced S states. See DOI: 10.1039/c4sc03720k Click here for additional data file.

    PubMed Central

    Krewald, Vera; Retegan, Marius; Cox, Nicholas; Messinger, Johannes; Lubitz, Wolfgang; DeBeer, Serena; Neese, Frank

    2015-01-01

    A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five Si states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S

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

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

    Wang, Xin

    1996-12-01

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

  13. Edge cracks in nickel and aluminium single crystals: A molecular dynamics study

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

    Chandra, Sagar, E-mail: sagarc@barc.gov.in; Chavan, V. M.; Patel, R. J.

    A molecular dynamics study of edge cracks in Ni and Al single crystals under mode-I loading conditions is presented. Simulations are performed using embedded-atom method potentials for Ni and Al at a temperature of 0.5 K. The results reveal that Ni and Al show different fracture mechanisms. Overall failure behavior of Ni is brittle, while fracture in Al proceeds through void nucleation and coalescence with a zig-zag pattern of crack growth. The qualitative nature of results is discussed in the context of vacancy-formation energies and surface energies of the two FCC metals.

  14. Experimental And Numerical Study Of CMC Leading Edges In Hypersonic Flows

    NASA Astrophysics Data System (ADS)

    Kuhn, Markus; Esser, Burkard; Gulhan, Ali; Dalenbring, Mats; Cavagna, Luca

    2011-05-01

    Future transportation concepts aim at high supersonic or hypersonic speeds, where the formerly sharp boundaries between aeronautic and aerospace applications become blurred. One of the major issues involved to high speed flight are extremely high aerothermal loads, which especially appear at the leading edges of the plane’s wings and at sharp edged air intake components of the propulsion system. As classical materials like metals or simple ceramics would thermally and structurally fail here, new materials have to be applied. In this context, lightweight ceramic matrix composites (CMC) seem to be prospective candidates as they are high-temperature resistant and offer low thermal expansion along with high specific strength at elevated temperature levels. A generic leading edge model with a ceramic wing assembly with a sweep back angle of 53° was designed, which allowed for easy leading edge sample integration of different CMC materials. The samples consisted of the materials C/C-SiC (non-oxide), OXIPOL and WHIPOX (both oxide) with a nose radius of 2 mm. In addition, a sharp edged C/C-SiC sample was prepared to investigate the nose radius influence. Overall, 13 thermocouples were installed inside the entire model to measure the temperature evolution at specific locations, whereby 5 thermocouples were placed inside the leading edge sample itself. In addition, non-intrusive techniques were applied for surface temperature measurements: An infrared camera was used to measure the surface temperature distribution and at specific spots, the surface temperature was also measured by pyrometers. Following, the model was investigated in DLR’s arc-heated facility L3K at a total enthalpy of 8.5 MJ/kg, Mach number of 7.8, different angles of attack and varying wing inclination angles. These experiments provide a sound basis for the simulation of aerothermally loaded CMC leading edge structures. Such fluid-structure coupled approaches have been performed by FOI, basing on a

  15. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

  16. 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

  17. Sorption of Eu(III) on attapulgite studied by batch, XPS, and EXAFS techniques.

    PubMed

    Fan, Q H; Tan, X L; Li, J X; Wang, X K; Wu, W S; Montavon, G

    2009-08-01

    The effects of pH, ionic strength, and temperature on sorption of Eu(III) on attapulgite were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The results indicated that the sorption of Eu(III) on attapulgite was strongly dependent on pH and ionic strength, and independent of temperature. In the presence of FA/HA, Eu(III) sorption was enhanced at pH < 4, decreased at pH range of 4-6, and then increased again at pH > 7. The X-ray photoelectron spectroscopy (XPS) analysis suggested that the sorption of Eu(III) might be expressed as is identical to X3Eu0, is identical to S(w)OHEu3+, and is identical to SOEu-OOC-/HA in the ternary Eu/HN/attapulgite system. The extended X-ray absorption fine structure (EXAFS) analysis of Eu-HA complexes indicated that the distances of d(Eu-O) decreased from 2.415 to 2.360 angstroms with increasing pH from 1.76 to 9.50, whereas the coordination number (N) decreased from approximately 9.94 to approximately 8.56. Different complexation species were also found for the different addition sequences of HA and Eu(III) to attapulgite suspension. The results are important to understand the influence of humic substances on Eu(III) behavior in the natural environment.

  18. EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

    NASA Astrophysics Data System (ADS)

    Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

    2010-12-01

    Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals

  19. 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

  20. Many-Body Effects in the Mesoscopic x-Ray Edge Problem

    NASA Astrophysics Data System (ADS)

    Hentschel, M.; R"Oder, G.; Ullmo, D.

    Many-body phenomena, a key interest in the investigation ofbulk solid state systems, are studied here in the context of the x-ray edge problem for mesoscopic systems. We investigate the many-body effects associated with the sudden perturbation following the x-ray excition of a core electron into the conduction band. For small systems with dimensions at the nanoscale we find considerable deviations from the well-understood metallic case where Anderson orthogonality catastrophe and the Mahan-Nozières-DeDominicis response cause characteristic deviations of the photoabsorption cross section from the naive expectation. Whereas the K-edge is typically rounded in metallic systems, we find a slightly peaked K-edge in generic mesoscopic systems with chaotic-coherent electron dynamics. Thus the behavior of the photoabsorption cross section at threshold depends on the system size and is different for the metallic and the mesoscopic case.

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

    NASA Astrophysics Data System (ADS)

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

    2018-06-01

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

  2. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

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

    Zubarev, Dmitry Yu.; Austin, Brian M.; Lester, William A. Jr.

    Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

  3. XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

    NASA Astrophysics Data System (ADS)

    Vlasenko, Valery G.; Vasilchenko, Igor S.; Pirog, Irina V.; Shestakova, Tatiana E.; Uraev, Ali I.; Burlov, Anatolii S.; Garnovskii, Alexander D.

    2007-02-01

    Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 Å. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

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

    EPA Pesticide Factsheets

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

  6. First principles study of edge carboxylated graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Abdelsalam, Hazem; Elhaes, Hanan; Ibrahim, Medhat A.

    2018-05-01

    The structure stability and electronic properties of edge carboxylated hexagonal and triangular graphene quantum dots are investigated using density functional theory. The calculated binding energies show that the hexagonal clusters with armchair edges have the highest stability among all the quantum dots. The binding energy of carboxylated graphene quantum dots increases by increasing the number of carboxyl groups. Our study shows that the total dipole moment significantly increases by adding COOH with the highest value observed in triangular clusters. The edge states in triangular graphene quantum dots with zigzag edges produce completely different energy spectrum from other dots: (a) the energy gap in triangular zigzag is very small as compared to other clusters and (b) the highest occupied molecular orbital is localized at the edges which is in contrast to other clusters where it is distributed over the cluster surface. The enhanced reactivity and the controllable energy gap by shape and edge termination make graphene quantum dots ideal for various nanodevice applications such as sensors. The infrared spectra are presented to confirm the stability of the quantum dots.

  7. Structure of assemblies of metal nanowires in mesoporous alumina membranes studied by EXAFS, XANES, X-ray diffraction and SAXS.

    PubMed

    Benfield, Robert E; Grandjean, Didier; Dore, John C; Esfahanian, Hamid; Wu, Zhonghua; Kröll, Michael; Geerkens, Marcus; Schmid, Günter

    2004-01-01

    Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic

  8. Built-up edge investigation in vibration drilling of Al2024-T6.

    PubMed

    Barani, A; Amini, S; Paktinat, H; Fadaei Tehrani, A

    2014-07-01

    Adding ultrasonic vibrations to drilling process results in an advanced hybrid machining process, entitled "vibration drilling". This study presents the design and fabrication of a vibration drilling tool by which both rotary and vibrating motions are applied to drill simultaneously. High frequency and low amplitude vibrations were generated by an ultrasonic transducer with frequency of 19.65 kHz. Ultrasonic transducer was controlled by a MPI ultrasonic generator with 3 kW power. The drilling tool and workpiece material were HSS two-flute twist drill and Al2024-T6, respectively. The aim of this study was investigating on the effect of ultrasonic vibrations on built-up edge, surface quality, chip morphology and wear mechanisms of drill edges. Therefore, these factors were studied in both vibration and ordinary drilling. Based on the achieved results, vibration drilling offers less built-up edge and better surface quality compared to ordinary drilling. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Ramp-edge structured tunneling devices using ferromagnet electrodes

    DOEpatents

    Kwon, Chuhee [Long Beach, CA; Jia, Quanxi [Los Alamos, NM

    2002-09-03

    The fabrication of ferromagnet-insulator-ferromagnet magnetic tunneling junction devices using a ramp-edge geometry based on, e.g., (La.sub.0.7 Sr.sub.0.3) MnO.sub.3, ferromagnetic electrodes and a SrTiO.sub.3 insulator is disclosed. The maximum junction magnetoresistance (JMR) as large as 23% was observed below 300 Oe at low temperatures (T<100 K). These ramp-edge junctions exhibited JMR of 6% at 200 K with a field less than 100 Oe.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  11. An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

    PubMed Central

    Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

    1982-01-01

    Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

  12. Structural instability and electronic localization in the 2:1 salts: The case of the Fabre and the (DMtTTF){2}CIO{4}salts

    NASA Astrophysics Data System (ADS)

    Ravy, S.; Foury-Leylekian, P.; Le Bolloc'h, D.; Pouget, J.-P.; Fabre, J. M.; Prado, R. J.; Lagarde, P.

    2004-04-01

    The charge ordering observed in the (TMTTF){2}X family has been studied by X-ray absorption spectroscopy. XANES measurements at the Sulfur K-edge show no evidence of charge disproportionation larger than 0.5 e, and EXAFS at the Phosphorus K-edge indicate no displacements of the PF{6} anion larger than 0.05 Å. The difficulty to observe a structural signature of this charge ordering is due to the triclinic symmetry of these salts. By contrast, in the monoclinic charge transfer salt (DMtTTF){2}ClO{4}, a screw axis symmetry constrains the molecular stacks to be uniform. In this real 1/4-filled system, charge localization is observed at about 150 K. We show that around this temperature an incommensurate modulation of reduced wave vector (0.58,0,-0.275) is stabilized. The transition is strongly hysteretic, but no long range order is established. We suggest that this modulation, which has the 4k{F} periodicity in the chain direction, stabilizes a local antiferroelectric state similar to the one previously observed in (TMTTF){2}SCN. Key words. Charge ordering, Structural phase transition.

  13. 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

  14. X-ray absorption edge spectroscopy and computational studies on LCuO2 species: Superoxide-Cu(II) versus peroxide-Cu(III) bonding.

    PubMed

    Sarangi, Ritimukta; Aboelella, Nermeen; Fujisawa, Kiyoshi; Tolman, William B; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2006-06-28

    The geometric and electronic structures of two mononuclear CuO2 complexes, [Cu(O2){HB(3-Ad-5-(i)Prpz)3}] (1) and [Cu(O2)(beta-diketiminate)] (2), have been evaluated using Cu K- and L-edge X-ray absorption spectroscopy (XAS) studies in combination with valence bond configuration interaction (VBCI) simulations and spin-unrestricted broken symmetry density functional theory (DFT) calculations. Cu K- and L-edge XAS data indicate the Cu(II) and Cu(III) nature of 1 and 2, respectively. The total integrated intensity under the L-edges shows that the 's in 1 and 2 contain 20% and 28% Cu character, respectively, indicative of very covalent ground states in both complexes, although more so in 1. Two-state VBCI simulations also indicate that the ground state in 2 has more Cu (/3d8) character. DFT calculations show that the in both complexes is dominated by O2(n-) character, although the O2(n-) character is higher in 1. It is shown that the ligand L plays an important role in modulating Cu-O2 bonding in these LCuO2 systems and tunes the ground states of 1 and 2 to have dominant Cu(II)-superoxide-like and Cu(III)-peroxide-like character, respectively. The contributions of ligand field (LF) and the charge on the absorbing atom in the molecule (Q(mol)M) to L- and K-edge energy shifts are evaluated using DFT and time-dependent DFT calculations. It is found that LF makes a dominant contribution to the edge energy shift, while the effect of Q(mol)M is minor. The charge on the Cu in the Cu(III) complex is found to be similar to that in Cu(II) complexes, which indicates a much stronger interaction with the ligand, leading to extensive charge transfer.

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  16. Molybdenum L-Edge XAS Spectra of MoFe Nitrogenase

    PubMed Central

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

    2015-01-01

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

  17. S K-edge XAS and DFT Calculations on Square Planar NiII-thiolate Complexes: Effects of Active and Passive H-bonding

    PubMed Central

    Dey, Abhishek; Green, Kayla N.; Jenkins, Roxanne M.; Jeffrey, Stephen P.; Darensbourg, Marcetta; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2008-01-01

    S K-edge XAS for a low-spin NiII-thiolate complex shows a 0.2 eV shift to higher pre-edge energy but no change in Ni-S bond covalency upon H-bonding. This is different from the H-bonding effect we observed in high spin FeIII-thiolate complexes where there is a significant decrease in Fe-S bond covalency but no change in energy due to H-bonding (Dey, A.; Okamura, T.-A.; Ueyama, N.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc.; 2005; 127, 12046-12053.). These differences were analyzed using DFT calculations and the results indicate that two different types of H-bonding interactions are possible in metal-thiolate systems. In the high-spin FeIII-thiolate case, the H-bonding involves a thiolate donor orbital which is also involved in bonding with the metal (active), while in the low-spin NiII-thiolate the orbital involved in H-bonding is non-bonding with respect to the M-S bonding (passive). The contributions of active and passive H-bonds to the reduction potential and Lewis acid properties of a metal center are evaluated. PMID:17949080

  18. Sorption of Metal Ions on Clay Minerals.

    PubMed

    Schlegel; Manceau; Chateigner; Charlet

    1999-07-01

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

  19. 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.

  20. Interpretation of thermal conductance of the ν =5 /2 edge

    NASA Astrophysics Data System (ADS)

    Simon, Steven H.

    2018-03-01

    Recent experiments [Banerjee et al., arXiv:1710.00492] have measured thermal conductance of the ν =5 /2 edge in a GaAs electron gas and found it to be quantized as K ≈5 /2 (in appropriate dimensionless units). This result is unexpected, as prior numerical work predicts that the ν =5 /2 state should be the anti-Pfaffian phase of matter, which should have quantized K =3 /2 . The purpose of this Rapid Communication is to propose a possible solution to this conflict: If the Majorana edge mode of the anti-Pfaffian does not thermally equilibrate with the other edge modes, then K =5 /2 is expected. I briefly discuss a possible reason for this nonequilibration and what should be examined further to determine if this is the case.

  1. Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

    DOE PAGES

    Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.; ...

    2017-12-27

    In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

  2. Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

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

    Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.

    In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

  3. 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

  4. 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

  5. Electronic structure-sunlight driven water splitting activity correlation of (Zn1-yGay)(O1-zNz).

    PubMed

    RajaAmbal, Sivaraman; Yadav, A K; Jha, S N; Bhattacharyya, D; Gopinath, Chinnnakonda S

    2014-11-21

    (Zn1-yGay)(O1-zNz) (y≤ 0.10; z≤ 0.15) solid solutions have been investigated for their electronic structure and visible light photocatalytic activity, and a correlation was found between them. (Zn1-yGay)(O1-zNz) with ZnO as the major component have been synthesized by a solution combustion method in 10 minutes using simple raw materials. The local structures of Zn K edge and Ga K edge, and changes in the chemical environment with the incorporation of Ga and N in ZnO were determined by EXAFS study. EXAFS and XRD results suggested the dissolution of GaN in the ZnO lattice. The homogeneity of the solid solution was demonstrated from HRTEM studies. Photoluminescence studies revealed the creation of a new band at the top of the ZnO valence band (VB), and thus the broadening of the VB of (Zn1-yGay)(O1-zNz) or a decrease in the band gap was attributed to the origin of visible light absorption. UV-Vis spectral studies showed light absorption up to 550 nm, which directly supports the VB broadening. Predominant oxygen vacancies and high photocorrosion observed for ZnO were fully suppressed for (Zn1-yGay)(O1-zNz), indicating the minimization of defects, and thus more sustainability under irradiation conditions. The bare solid solution exhibited reasonable and promising activity for solar hydrogen evolution and photoelectrochemical current generation at 0 V. The present work explained factors such as the preparation method, single phase structure with the stabilization of integral parts, homogeneity in the structure, compensation of oxygen vacancies, and suppression of the density of recombination centres that play a pivotal role in realizing solar energy harvesting.

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

    PubMed

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

    2016-05-04

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

  7. A Study of Two Dimensional Tapered Periodic Edge Treatments to Reduce Wideband Edge Diffraction

    DTIC Science & Technology

    1993-12-01

    the Air Force Institute of Technology Air University In Partial Fulfillment of the Acce, ion Fur Requirements for the Degree of s ,,4- Master of Science...edge cards . Another major area of study for these periodic tapers would be in the reduction in edge scattering from a finite size radome. For better...I c), C) C C":)z6 ý2--10. 0. 10.20 TIME IN NANOSECS 2. 4. 6. 8. 10. 12. 14. 16. 18. c:) CD .J6 cbCZ- 6 •C5 C u’) r’ LLcb _ cVV • 00 2. 4. 6. 8. 10. 12

  8. 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.

  9. 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.

  10. 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.

  11. Distance Domination Number of Graphs Resulting from Edge Comb Product

    NASA Astrophysics Data System (ADS)

    Slamin; Dafik; Angger Waspodo, Gembong

    2018-05-01

    Let G be a simple, finite and connected graph with a vertex-set V (G) and an edge-set E(G). For an integer 1 ≤ k ≤ diam (G), a distance k-dominating set of a connected graph G is a set S of vertices of G such that every vertex of V (G)\\S is at distance at most k from some vertex of S. The k-domination number of G, denoted by γk (G), is the minimum cardinality of a k-dominating set of G. In this paper, we determine the exact value of k-domination number of graphs resulting from an edge comb product of two graphs G 1 and G 2, where G 1 is a wheel, a friendship graph, or a triangular book and G 2 is a cycle.

  12. Validation and Analysis of Numerical Results for a Two-Pass Trapezoidal Channel With Different Cooling Configurations of Trailing Edge.

    PubMed

    Siddique, Waseem; El-Gabry, Lamyaa; Shevchuk, Igor V; Fransson, Torsten H

    2013-01-01

    High inlet temperatures in a gas turbine lead to an increase in the thermal efficiency of the gas turbine. This results in the requirement of cooling of gas turbine blades/vanes. Internal cooling of the gas turbine blade/vanes with the help of two-pass channels is one of the effective methods to reduce the metal temperatures. In particular, the trailing edge of a turbine vane is a critical area, where effective cooling is required. The trailing edge can be modeled as a trapezoidal channel. This paper describes the numerical validation of the heat transfer and pressure drop in a trapezoidal channel with and without orthogonal ribs at the bottom surface. A new concept of ribbed trailing edge has been introduced in this paper which presents a numerical study of several trailing edge cooling configurations based on the placement of ribs at different walls. The baseline geometries are two-pass trapezoidal channels with and without orthogonal ribs at the bottom surface of the channel. Ribs induce secondary flow which results in enhancement of heat transfer; therefore, for enhancement of heat transfer at the trailing edge, ribs are placed at the trailing edge surface in three different configurations: first without ribs at the bottom surface, then ribs at the trailing edge surface in-line with the ribs at the bottom surface, and finally staggered ribs. Heat transfer and pressure drop is calculated at Reynolds number equal to 9400 for all configurations. Different turbulent models are used for the validation of the numerical results. For the smooth channel low-Re k-ɛ model, realizable k-ɛ model, the RNG k-ω model, low-Re k-ω model, and SST k-ω models are compared, whereas for ribbed channel, low-Re k-ɛ model and SST k-ω models are compared. The results show that the low-Re k-ɛ model, which predicts the heat transfer in outlet pass of the smooth channels with difference of +7%, underpredicts the heat transfer by -17% in case of ribbed channel compared to

  13. 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

  14. Edge ohmic heating and improved confinement on HT-6M Tokamak

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

    Gao, X.

    1995-04-01

    An improved confinement has been observed on HT-6M tokamak after application of Edge Ohmic Heating (EOH) which makes plasma current rapidly ramp up from an initial steady state (I{sub p}=55 kA) within a small time scale (0.4 ms) to a second steady state (I{sub p}=60 kA) with a ramp rate of 12 MA/sec. The improved confinement is characterized by (a) increased average density n{sub e}; (b) reduced H{sub alpha} radiation; (c) reduced density fluctuations both in the center and at the edge; (d) a steeper n{sub e} and T{sub e} profile at the edge; (e) the changed profiles of plasmamore » parameters n{sub e}(r), q(r) and j(r); (f) transferred the oscillation modes of the soft-X ray signals from Mirnov fluctuation (12 kHz) to sawtooth oscillation (1.7 kHz). The changes of edge fluctuation, radial electric field and bremsstrahlung during EOH were measured and discussed in details. The measured values of {beta}{sub p}+l{sub i}/2 and soft-X ray sawtooth inversion radius implied the anomalous current penetration. 10 refs., 2 figs.« less

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

    PubMed

    Zhang, Renqin; McEwen, Jean-Sabin

    2018-05-22

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

  16. A k · p treatment of edge states in narrow 2D topological insulators, with standard boundary conditions for the wave function and its derivative.

    PubMed

    Klipstein, P C

    2018-07-11

    For 2D topological insulators with strong electron-hole hybridization, such as HgTe/CdTe quantum wells, the widely used 4  ×  4 k · p Hamiltonian based on the first electron and heavy hole sub-bands yields an equal number of physical and spurious solutions, for both the bulk states and the edge states. For symmetric bands and zero wave vector parallel to the sample edge, the mid-gap bulk solutions are identical to the edge solutions. In all cases, the physical edge solution is exponentially localized to the boundary and has been shown previously to satisfy standard boundary conditions for the wave function and its derivative, even in the limit of an infinite wall potential. The same treatment is now extended to the case of narrow sample widths, where for each spin direction, a gap appears in the edge state dispersions. For widths greater than 200 nm, this gap is less than half of the value reported for open boundary conditions, which are called into question because they include a spurious wave function component. The gap in the edge state dispersions is also calculated for weakly hybridized quantum wells such as InAs/GaSb/AlSb. In contrast to the strongly hybridized case, the edge states at the zone center only have pure exponential character when the bands are symmetric and when the sample has certain characteristic width values.

  17. Mineral transformation controls speciation and pore-fluid transmission of contaminants in waste-weathered Hanford sediments

    NASA Astrophysics Data System (ADS)

    Perdrial, Nicolas; Thompson, Aaron; O'Day, Peggy A.; Steefel, Carl I.; Chorover, Jon

    2014-09-01

    Portions of the Hanford Site (WA, USA) vadose zone were subjected to weathering by caustic solutions during documented releases of high level radioactive waste (containing Sr, Cs and I) from leaking underground storage tanks. Previous studies have shown that waste-sediment interactions can promote variable incorporation of contaminants into neo-formed mineral products (including feldspathoids and zeolites), but processes regulating the subsequent contaminant release from these phases into infiltrating background pore waters remain poorly known. In this paper, reactive transport experiments were conducted with Hanford sediments previously weathered for one year in simulated hyper-alkaline waste solutions containing high or low 88Sr, 127I, and 133Cs concentrations, with or without CO2(aq). These waste-weathered sediments were leached in flow-through column experiments with simulated background pore water (characteristic of meteoric recharge) to measure contaminant release from solids formed during waste-sediment interaction. Contaminant sorption-desorption kinetics and mineral transformation reactions were both monitored using continuous-flow and wet-dry cycling regimes for ca. 300 pore volumes. Less than 20% of contaminant 133Cs and 88Sr mass and less than 40% 127I mass were released over the course of the experiment. To elucidate molecular processes limiting contaminant release, reacted sediments were studied with micro- (TEM and XRD) and molecular- (Sr K-edge EXAFS) scale methods. Contaminant dynamics in column experiments were principally controlled by rapid dissolution of labile solids and competitive exchange reactions. In initially feldspathoidic systems, time-dependent changes in the local zeolitic bonding environment observed with X-ray diffraction and EXAFS are responsible for limiting contaminant release. Linear combination fits and shell-by-shell analysis of Sr K-edge EXAFS data revealed modification in Sr-Si/Al distances within the zeolite cage. Wet

  18. Study Abroad: A Competitive Edge for Women?

    ERIC Educational Resources Information Center

    Opper, Susan

    1991-01-01

    Studies effects of study abroad among 172 female and 217 male graduates in the United Kingdom, France, and the Federal Republic of Germany between 1980 and 1984. Finds study abroad expedites obtaining job interviews but was of little advantage in securing employment for either sex. Finds degree credential provides a competitive edge. (NL)

  19. How Does CeIII Nitrate Dissolve in a Protic Ionic Liquid? A Combined Molecular Dynamics and EXAFS Study.

    PubMed

    Serva, Alessandra; Migliorati, Valentina; Spezia, Riccardo; D'Angelo, Paola

    2017-06-22

    A diluted solution of Ce(NO 3 ) 3 in the protic ionic liquid (IL) ethylammonium nitrate (EAN) was investigated using molecular dynamics (MD) simulations and extended X-ray absorption fine structure (EXAFS) spectroscopy. For the first time polarizable effects were included in the MD force field to describe a heavy metal ion in a protic IL, but, unlike water, they were found to be unessential. The Ce III ion first solvation shell is formed by nitrate ions arranged in an icosahedral structure, and an equilibrium between monodentate and bidentate ligands is present in the solution. By combining distance and angular distribution functions it was possible to unambiguously identify this peculiar coordination geometry around the ions dissolved in solution. The metal ions are solvated within the polar domains of the EAN nanostructure and the dissolved salt induces almost no reorganization of the pre-existing structure of EAN upon solubilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

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

    Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

    2014-05-01

    Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

  1. Edge-oriented dual-dictionary guided enrichment (EDGE) for MRI-CT image reconstruction.

    PubMed

    Li, Liang; Wang, Bigong; Wang, Ge

    2016-01-01

    In this paper, we formulate the joint/simultaneous X-ray CT and MRI image reconstruction. In particular, a novel algorithm is proposed for MRI image reconstruction from highly under-sampled MRI data and CT images. It consists of two steps. First, a training dataset is generated from a series of well-registered MRI and CT images on the same patients. Then, an initial MRI image of a patient can be reconstructed via edge-oriented dual-dictionary guided enrichment (EDGE) based on the training dataset and a CT image of the patient. Second, an MRI image is reconstructed using the dictionary learning (DL) algorithm from highly under-sampled k-space data and the initial MRI image. Our algorithm can establish a one-to-one correspondence between the two imaging modalities, and obtain a good initial MRI estimation. Both noise-free and noisy simulation studies were performed to evaluate and validate the proposed algorithm. The results with different under-sampling factors show that the proposed algorithm performed significantly better than those reconstructed using the DL algorithm from MRI data alone.

  2. Studies on absorption coefficient near edge of multi elements

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  3. Modeling the Acid-Base Properties of Montmorillonite Edge Surfaces.

    PubMed

    Tournassat, Christophe; Davis, James A; Chiaberge, Christophe; Grangeon, Sylvain; Bourg, Ian C

    2016-12-20

    The surface reactivity of clay minerals remains challenging to characterize because of a duality of adsorption surfaces and mechanisms that does not exist in the case of simple oxide surfaces: edge surfaces of clay minerals have a variable proton surface charge arising from hydroxyl functional groups, whereas basal surfaces have a permanent negative charge arising from isomorphic substitutions. Hence, the relationship between surface charge and surface potential on edge surfaces cannot be described using the Gouy-Chapman relation, because of a spillover of negative electrostatic potential from the basal surface onto the edge surface. While surface complexation models can be modified to account for these features, a predictive fit of experimental data was not possible until recently, because of uncertainty regarding the densities and intrinsic pK a values of edge functional groups. Here, we reexamine this problem in light of new knowledge on intrinsic pK a values obtained over the past decade using ab initio molecular dynamics simulations, and we propose a new formalism to describe edge functional groups. Our simulation results yield reasonable predictions of the best available experimental acid-base titration data.

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

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

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

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

    DOE PAGES

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

    2017-06-06

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

  6. Static Extended Trailing Edge for Lift Enhancement: Experimental and Computational Studies

    NASA Technical Reports Server (NTRS)

    Liu, Tianshu; Montefort; Liou, William W.; Pantula, Srinivasa R.; Shams, Qamar A.

    2007-01-01

    A static extended trailing edge attached to a NACA0012 airfoil section is studied for achieving lift enhancement at a small drag penalty. It is indicated that the thin extended trailing edge can enhance the lift while the zero-lift drag is not significantly increased. Experiments and calculations are conducted to compare the aerodynamic characteristics of the extended trailing edge with those of Gurney flap and conventional flap. The extended trailing edge, as a simple mechanical device added on a wing without altering the basic configuration, has a good potential to improve the cruise flight efficiency.

  7. Effect of molecular intercalation on the local structure of superconducting Nax(NH3)yMoSe2 system

    NASA Astrophysics Data System (ADS)

    Simonelli, L.; Paris, E.; Wakita, T.; Marini, C.; Terashima, K.; Miao, X.; Olszewski, W.; Ramanan, N.; Heinis, D.; Kubozono, Y.; Yokoya, T.; Saini, N. L.

    2017-12-01

    We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature (ΘE) of Mo-Mo distance hardly changes (∼264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of ΘE from ∼364 K to ∼350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

  8. Revisiting the hydration structure of aqueous Na +

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

    Galib, M.; Baer, M. D.; Skinner, L. B.

    In this paper, a combination of theory, X-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) are used to probe the hydration structure of aqueous Na +. The high spatial resolution of the XRD measurements corresponds to Qmax = 24 Å –1 while the first-reported Na K-edge EXAFS measurements have a spatial resolution corresponding to 2k = Qmax = 16 Å –1. Both provide an accurate measure of the shape and position of the first peak in the Na–O pair distribution function, g NaO(r). The measured Na–O distances of 2.384 ± 0.003 Å (XRD) and 2.37 ± 0.024 Åmore » (EXAFS) are in excellent agreement. These measurements show a much shorter Na–O distance than generally reported in the experimental literature (Na–O avg ~ 2.44 Å) although the current measurements are in agreement with recent neutron diffraction measurements. The measured Na–O coordination number from XRD is 5.5 ± 0.3. The measured structure is compared with both classical and first-principles density functional theory (DFT) simulations. Both of the DFT-based methods, revPBE and BLYP, predict a Na–O distance that is too long by about 0.05 Å with respect to the experimental data (EXAFS and XRD). The inclusion of dispersion interactions (–D3 and –D2) significantly worsens the agreement with experiment by further increasing the Na–O distance by 0.07 Å. In contrast, the use of a classical Na–O Lennard-Jones potential with SPC/E water accurately predicts the Na–O distance as 2.39 Å although the Na–O peak is over-structured with respect to experiment.« less

  9. Revisiting the hydration structure of aqueous Na +

    DOE PAGES

    Galib, M.; Baer, M. D.; Skinner, L. B.; ...

    2017-02-27

    In this paper, a combination of theory, X-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) are used to probe the hydration structure of aqueous Na +. The high spatial resolution of the XRD measurements corresponds to Qmax = 24 Å –1 while the first-reported Na K-edge EXAFS measurements have a spatial resolution corresponding to 2k = Qmax = 16 Å –1. Both provide an accurate measure of the shape and position of the first peak in the Na–O pair distribution function, g NaO(r). The measured Na–O distances of 2.384 ± 0.003 Å (XRD) and 2.37 ± 0.024 Åmore » (EXAFS) are in excellent agreement. These measurements show a much shorter Na–O distance than generally reported in the experimental literature (Na–O avg ~ 2.44 Å) although the current measurements are in agreement with recent neutron diffraction measurements. The measured Na–O coordination number from XRD is 5.5 ± 0.3. The measured structure is compared with both classical and first-principles density functional theory (DFT) simulations. Both of the DFT-based methods, revPBE and BLYP, predict a Na–O distance that is too long by about 0.05 Å with respect to the experimental data (EXAFS and XRD). The inclusion of dispersion interactions (–D3 and –D2) significantly worsens the agreement with experiment by further increasing the Na–O distance by 0.07 Å. In contrast, the use of a classical Na–O Lennard-Jones potential with SPC/E water accurately predicts the Na–O distance as 2.39 Å although the Na–O peak is over-structured with respect to experiment.« less

  10. Papers from U.S. Department of Energy Science Undergraduate Laboratory Internship Program (SULI) 2010

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

    Not Available

    2011-06-22

    The solvation sphere of halides in water has been investigated using a combination of extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis techniques. The results have indicated that I{sup -} and Br{sup -} both have an asymmetric, 8 water molecule primary solvation spheres. These spheres are identical, with the Br{sup -} sphere about .3 {angstrom} smaller than the I{sup -} sphere. This study utilized near-edge analysis to supplement EXAFS analysis which suffers from signal dampening/broadening due to thermal noise. This paper has reported on the solvation first sphere of I{sup -} and Br{sup -} inmore » water. Using EXAFS and XANES analysis, strong models which describe the geometric configuration of water molecules coordinated to a central anion have been developed. The combination of these techniques has provided us with a more substantiated argument than relying solely on one or the other. An important finding of this study is that the size of the anion plays a smaller role than previously assumed in determining the number of coordinating water molecules. Further experimental and theoretical investigation is required to understand why the size of the anion plays a minor role in determining the number of water molecules bound.« less

  11. Variation in throughfall deposition across a deciduous beech (Fagus sylvatica L.) forest edge in Flanders.

    PubMed

    Devlaeminck, Rebecca; De Schrijver, An; Hermy, Martin

    2005-01-20

    Throughfall deposition and canopy exchange of acidifying and eutrophying compounds and major base cations were studied by means of throughfall analysis in a deciduous beech (Fagus sylvatica L.) forest edge in Belgium over a period of 1 year. Throughfall fluxes of Cl(-), NH(4)(+) and Na(+) were significantly elevated at the forest edge compared to the forest interior. As no edge effect on throughfall water volume could be detected, the observed edge enhancement effects were mainly due to dry deposition and canopy exchange patterns. Indeed, there was an elevated dry deposition of Cl(-), Na(+), K(+), Ca(2+) and Mg(2+) up to 50 m from the field/forest border. Within the forest, throughfall and dry deposition of SO(4)(2-) were highly variable and no significant differences were observed between the forest edge and the forest interior. Leaching of K(+) and Ca(2+) was reduced in the forest edge up to a distance of 30 m from the border. The measured nitrogen and acidic depositions far exceeded the current Flemish critical loads with respect to the protection of biodiversity in forests, especially at the forest edge. This points to an urgent need for controlling emissions as well as the need to consider the elevated deposition load in forest edges when calculating the critical loads in forests.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  13. 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

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

    PubMed Central

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

    2016-01-01

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

  15. Adiabatic Demagnetization Refrigerator Field Mapping and Shielding Models for a 70 mK Superconducting Transition Edge Sensor Array and Associated Electronics

    NASA Astrophysics Data System (ADS)

    Ladner, D. R.; Martinez-Galarce, D. S.; McCammon, D.

    2006-04-01

    An X-ray detection instrument to be flown on a sounding rocket experiment (the Advanced Technology Solar Spectroscopic Imager - ATSSI) for solar physics observations is being developed by the Lockheed Martin Solar and Astrophysics Laboratory (LMSAL). The detector is a novel class of microcalorimeter, a superconducting Transition-Edge Sensor (TES), that coupled with associated SQUID and feedback electronics requires high temperature stability at ~70 mK to resolve the energy of absorbed X-ray photons emitted from the solar corona. The cooling system incorporates an existing Adiabatic Demagnetization Refrigerator (ADR) developed at the University of Wisconsin (UW), which was previously flown to study the diffuse cosmic X-ray background. The Si thermistor detectors for that project required 130 K shielded JFET electronic components that are much less sensitive to the external field of the ADR solenoid than are the 1st (~70 mK) and 2nd (~2 K) SQUID stages used with TESs for solar observations. Modification of the Wisconsin ADR design, including TES focal plane and electronics re-positioning, therefore requires a tradeoff between the existing ADR solenoid nulling coil geometry and a low mass passive solenoid shield, while preserving the vibration isolation features of the existing design. We have developed models to accurately compute the magnetic field with and without shielding or nulling coils at critical locations to guide the re-design of the detector subsystem. The models and their application are described.

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

    PubMed

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

    2017-06-21

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

  17. 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.

  18. Polarity control of h-BN nanoribbon edges by strain and edge termination.

    PubMed

    Yamanaka, Ayaka; Okada, Susumu

    2017-03-29

    We studied the polarity of h-BN nano-flakes in terms of their edge geometries, edge hydrogen termination, and uniaxial strain by evaluating their electrostatic potential using density functional theory. Our calculations have shown that the polarity of the nanoribbons is sensitive to their edge shape, edge termination, and uniaxial tensile strain. Polarity inversion of the ribbons can be induced by controlling the hydrogen concentration at the edges and the uniaxial tensile strain. The polarity inversion indicates that h-BN nanoribbons can exhibit non-polar properties at a particular edge hydrogen concentration and tensile strain, even though the nanoribbons essentially have polarity at the edge. We also found that the edge angle affects the polarity of nanoribbons with hydrogenated edges.

  19. Temperature dependence of interfacial structures and acidity of clay edge surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Xiandong; Lu, Xiancai; Cheng, Jun; Sprik, Michiel; Wang, Rucheng

    2015-07-01

    In the pursuit of a microscopic understanding of the effects of temperature on the surface reactivity of clay minerals, we conducted first principles molecular dynamics (FPMD) simulations to study the interfacial structures and acidity of clay edge surfaces at elevated temperatures. The common edge surfaces ((0 1 0) and (1 1 0) types) of phyllosilicates were investigated at 348 K and 423 K, and the results were compared with those previously derived at ambient conditions. We found that the stable surface sites are the same as at ambient conditions, including tbnd Al(OH2)2 (6-fold Al), tbnd Al(OH2) (5-fold Al) and tbnd Si(OH) on the (0 1 0) facet, and tbnd Al(OH2), tbnd Al(OH)Sitbnd and tbnd Si(OH) on the (1 1 0) surface. The FPMD-based vertical energy gap technique was applied to compute the acidity constants of edge sites and the resulting pKa values show a decreasing trend with temperature. The results demonstrate that although changes in the point of zero charge of the entire material are insignificant up to 348 K, the decrease in surface pKa can be 3 pKa units, while it can be as large as 6 pKa units up to 423 K. The derived interface structures and pKa values can be used in future experimental and modeling research, e.g., in interpreting experiments and predicting the surface complexation of metal cations and organics. This study therefore provides a physical basis for investigating the interfacial processes of clay minerals in environments that experience elevated P-T conditions, such as sedimentary basins and geological nuclear waste repositories.

  20. Evaluation of potential substrates for restenosis and thrombosis in overlapped versus edge-to-edge juxtaposed bioabsorbable scaffolds: Insights from a computed fluid dynamic study.

    PubMed

    Rigatelli, Gianluca; Zuin, Marco; Dell'Avvocata, Fabio; Cardaioli, Paolo; Vassiliev, Dobrin; Ferenc, Miroslaw; Nghia, Nguyen Tuan; Nguyen, Thach; Foin, Nicholas

    2018-04-01

    Multiple BRSs and specifically the Absorb scaffold (BVS) (Abbott Vascular, Santa Clara, CA USA) have been often used to treat long diffuse coronary artery lesions. We evaluate by a computational fluid dynamic(CFD) study the impact on the intravascular fluid rheology on multiple bioabsorbable scaffolds (BRS) by standard overlapping versus edge-to-edge technique. We simulated the treatment of a real long significant coronary lesion (>70% luminal narrowing) involving the left anterior descending artery (LAD) treated with a standard or edge-to-edge technique, respectively. Simulations were performed after BVS implantations in two different conditions: 1) Edge-to-edge technique, where the scaffolds are kissed but not overlapped resulting in a luminal encroachment of 0.015cm (150μm); 2) Standard overlapping, where the scaffolds are overlapped resulting in a luminal encroachment of 0.030cm (300μm). After positioning the BVS across the long lesion, the implantation procedure was performed in-silico following all the usual procedural steps. Analysis of the wall shear stress (WSS) suggested that at the vessel wall level the WSS were lower in the overlapping zones overlapping compared to the edge-to-edge zone (∆=0.061Pa, p=0.01). At the struts level the difference between the two WSS was more striking (∆=1.065e-004 p=0.01) favouring the edge-to-edge zone. Our study suggested that at both vessel wall and scaffold struts levels, there was lowering WSS when multiple BVS were implanted with the standard overlapping technique compared to the "edge-to-edge" technique. This lower WSS might represent a substrate for restenosis, early and late BVS thrombosis, potentially explaining at least in part the recent evidences of devices poor performance. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe 4 S 4 ] Site in EndoIII and MutY

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

    Ha, Yang; Arnold, Anna R.; Nuñez, Nicole N.

    S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe 4S 4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe–S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron–thiolate and iron–sulfide bonds would stabilize the oxidized state of the [Fe 4S 4] clusters. Our results are compared to those on previously studied [Fe 4S 4] model complexes, ferredoxin (Fd), and to new data on high-potential iron–sulfur protein (HiPIP). A limited decrease in covalency ismore » observed upon removal of solvent water from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe 4S 4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron–sulfur bonds. Furthermore, in EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.« less

  2. Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe 4 S 4 ] Site in EndoIII and MutY

    DOE PAGES

    Ha, Yang; Arnold, Anna R.; Nuñez, Nicole N.; ...

    2017-07-18

    S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe 4S 4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe–S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron–thiolate and iron–sulfide bonds would stabilize the oxidized state of the [Fe 4S 4] clusters. Our results are compared to those on previously studied [Fe 4S 4] model complexes, ferredoxin (Fd), and to new data on high-potential iron–sulfur protein (HiPIP). A limited decrease in covalency ismore » observed upon removal of solvent water from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe 4S 4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron–sulfur bonds. Furthermore, in EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.« less

  3. Plasma-edge studies using carbon resistance probes

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

    Wampler, W.R.

    1984-01-01

    Characterization of erosion and hydrogen-recycling processes occurring at the edge of magnetically confined plasmas requires knowledge of the energy and flux of hydrogen isotopes incident on the materials. A new plasma-edge probe technique, the carbon resistance probe, has been developed to obtain this information. This technique uti

  4. Solution structures of chloroquine-ferriheme complexes modeled using MD simulation and investigated by EXAFS spectroscopy.

    PubMed

    Kuter, David; Streltsov, Victor; Davydova, Natalia; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

    2016-01-01

    The interaction of chloroquine (CQ) and the μ-oxo dimer of iron(III) protoporphyrin IX (ferriheme) in aqueous solution was modeled using molecular dynamics (MD) simulations. Two models of the CQ-(μ-oxo ferriheme) complex were investigated, one involving CQ π-stacked with an unligated porphyrin face of μ-oxo ferriheme and the other in which CQ was docked between the two porphyrin rings. The feasibility of both models was tested by fitting computed structures to the experimental extended X-ray absorption fine structure (EXAFS) spectrum of the CQ-(μ-oxo ferriheme) complex in frozen aqueous solution. The docked model produced better agreement with experimental data, suggesting that this is the more likely structure in aqueous solution. The EXAFS fit indicated a longer than expected Fe-O bond of 1.87Å, accounting for the higher than expected magnetic moment of the complex. As a consequence, the asymmetric Fe-O-Fe stretch shifts much lower in frequency and was identified in the precipitated solid at 744cm(-1) with the aid of the O(18) isomer shift. Three important CQ-ferriheme interactions were identified in the docked structure. These were a hydrogen bond between the oxide bridge of μ-oxo ferriheme and the protonated quinolinium nitrogen atom of CQ; π-stacking between the quinoline ring of CQ and the porphyrin rings; and a close contact between the 7-chloro substituent of CQ and the porphyrin methyl hydrogen atoms. These interactions can be used to rationalize previously observed structure-activity relationships for quinoline-ferriheme association. Copyright © 2015 Elsevier Inc. All rights reserved.

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

    Kaspar, Tiffany C.; Sushko, Peter V.; Bowden, Mark E.

    Epitaxial thin films of Cr2-xTixO3 were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) for 0.04 ≤ x ≤ 0.26. Ti speciation is verified by both x-ray photoelectron spectroscopy (XPS) and Ti K-edge x-ray absorption near-edge spectroscopy (XANES) to be Ti4+. Substitution of Ti for Cr in the corundum lattice is confirmed by modeling of the Ti K-edge extended x-ray absorption fine structure (EXAFS). Room temperature electrical transport measurements confirm the highly insulating nature of Ti-doped Cr2O3, despite the presence of aliovalent Ti4+. The resistivity of highly pure, undoped Cr2O3 was measured to be three orders of magnitude higher than formore » Ti-doped Cr2O3. Although the formation of Cr vacancies in Ti-doped Cr2O3 is found by density functional theory (DFT) calculations to be the energetically preferable defect compensation mechanism to maintain charge neutrality, an analysis of the XPS and EXAFS data reveal the presence of both Cr vacancies and oxygen interstitials at intermediate and high Ti concentrations, with a weak trend towards Cr vacancies as the Ti concentration increases. At low Ti concentrations, a strong dependence of the XPS Ti 2p core level peak width on concentration is observed. This dependence is attributed to the presence of widely spaced Ti dopants, which renders compensation of two or three Ti by a single oxygen interstitial or Cr vacancy, respectively, less probable. Instead, defect clusters of unknown type occur, although they may involve Cr vacancies. The defect compensation model developed here provides insight into previous, conflicting reports of n-type versus p-type conductivity in Ti-doped Cr2O3 at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum-structure oxides.« less

  6. Toward edge minability for role mining in bipartite networks

    NASA Astrophysics Data System (ADS)

    Dong, Lijun; Wang, Yi; Liu, Ran; Pi, Benjie; Wu, Liuyi

    2016-11-01

    Bipartite network models have been extensively used in information security to automatically generate role-based access control (RBAC) from dataset. This process is called role mining. However, not all the topologies of bipartite networks are suitable for role mining; some edges may even reduce the quality of role mining. This causes unnecessary time consumption as role mining is NP-hard. Therefore, to promote the quality of role mining results, the capability that an edge composes roles with other edges, called the minability of edge, needs to be identified. We tackle the problem from an angle of edge importance in complex networks; that is an edge easily covered by roles is considered to be more important. Based on this idea, the k-shell decomposition of complex networks is extended to reveal the different minability of edges. By this way, a bipartite network can be quickly purified by excluding the low-minability edges from role mining, and thus the quality of role mining can be effectively improved. Extensive experiments via the real-world datasets are conducted to confirm the above claims.

  7. Study of supersonic wings employing the attainable leading-edge thrust concept

    NASA Technical Reports Server (NTRS)

    Middleton, W. D.

    1982-01-01

    A theoretical study was made of supersonic wing geometries at Mach 1.8, using the attainable leading-edge thrust concept. The attainable thrust method offers a powerful means to improve overall aerodynamic efficiency by identifying wing leading-edge geometries that promote attached flow and by defining a local angle-of-attack range over which attached flow may be obtained. The concept applies to flat and to cambered wings, which leads to the consideration of drooped-wing leading edges for attached flow at high lift coefficients.

  8. Observation of topological edge states of acoustic metamaterials at subwavelength scale

    NASA Astrophysics Data System (ADS)

    Dai, Hongqing; Jiao, Junrui; Xia, Baizhan; Liu, Tingting; Zheng, Shengjie; Yu, Dejie

    2018-05-01

    Topological states are of key importance for acoustic wave systems owing to their unique transport properties. In this study, we develop a hexagonal array of hexagonal columns with Helmholtz resonators to obtain subwavelength Dirac cones. Rotation operations are performed to open the Dirac cones and obtain acoustic valley vortex states. In addition, we calculate the angular-dependent frequencies for the band edges at the K-point. Through a topological phase transition, the topological phase of pattern A can change into that of pattern B. The calculations for the bulk dispersion curves show that the acoustic metamaterials exhibit BA-type and AB-type topological edge states. Experimental results demonstrate that a sound wave can transmit well along the topological path. This study could reveal a simple approach to create acoustic topological edge states at the subwavelength scale.

  9. Structure and stability of pyrophyllite edge surfaces: Effect of temperature and water chemical potential

    NASA Astrophysics Data System (ADS)

    Kwon, Kideok D.; Newton, Aric G.

    2016-10-01

    The surfaces of clay minerals, which are abundant in atmospheric mineral dust, serve as an important medium to catalyze ice nucleation. The lateral edge surface of 2:1 clay minerals is postulated to be a potential site for ice nucleation. However, experimental investigations of the edge surface structure itself have been limited compared to the basal planes of clay minerals. Density functional theory (DFT) computational studies have provided insights into the pyrophyllite edge surface. Pyrophyllite is an ideal surrogate mineral for the edge surfaces of 2:1 clay minerals as it possesses no or little structural charge. Of the two most-common hydrated edge surfaces, the AC edge, (1 1 0) surface in the monoclinic polytype notation, is predicted to be more stable than the B edge, (0 1 0) surface. These stabilities, however, were determined based on the total energies calculated at 0 K and did not consider environmental effects such as temperature and humidity. In this study, atomistic thermodynamics based on periodic DFT electronic calculations was applied to examine the effects of environmental variables on the structure and thermodynamic stability of the common edge surfaces in equilibrium with bulk pyrophyllite and water vapor. We demonstrate that the temperature-dependent vibrational energy of sorbed water molecules at the edge surface is a significant component of the surface free energy and cannot be neglected when determining the surface stability of pyrophyllite. The surface free energies were calculated as a function of temperature from 240 to 600 K and water chemical potential corresponding to conditions from ultrahigh vacuum to the saturation vapor pressure of water. We show that at lower water chemical potentials (dry conditions), the AC and B edge surfaces possessed similar stabilities; at higher chemical potentials (humid conditions) the AC edge surface was more stable than the B edge surface. At high temperatures, both surfaces showed similar stabilities

  10. The existence of topological edge states in honeycomb plasmonic lattices

    NASA Astrophysics Data System (ADS)

    Wang, Li; Zhang, Ruo-Yang; Xiao, Meng; Han, Dezhuan; Chan, C. T.; Wen, Weijia

    2016-10-01

    In this paper, we investigate the band properties of 2D honeycomb plasmonic lattices consisting of metallic nanoparticles. By means of the coupled dipole method and quasi-static approximation, we theoretically analyze the band structures stemming from near-field interaction of localized surface plasmon polaritons for both the infinite lattice and ribbons. Naturally, the interaction of point dipoles decouples into independent out-of-plane and in-plane polarizations. For the out-of-plane modes, both the bulk spectrum and the range of the momentum k ∥ where edge states exist in ribbons are similar to the electronic bands in graphene. Nevertheless, the in-plane polarized modes show significant differences, which do not only possess additional non-flat edge states in ribbons, but also have different distributions of the flat edge states in reciprocal space. For in-plane polarized modes, we derived the bulk-edge correspondence, namely, the relation between the number of flat edge states at a fixed {k}\\parallel , Zak phases of the bulk bands and the winding number associated with the bulk Hamiltonian, and verified it through four typical ribbon boundaries, i.e. zigzag, bearded zigzag, armchair, and bearded armchair. Our approach gives a new topological understanding of edge states in such plasmonic systems, and may also apply to other 2D ‘vector wave’ systems.

  11. Orientation of Calcium in the Mn4Ca Cluster of the Oxygen-Evolving Complex Determined Using Polarized Strontium EXAFS of Photosystem II Membranes†

    PubMed Central

    Cinco, Roehl M.; Robblee, John H.; Messinger, Johannes; Fernandez, Carmen; Holman, Karen L. McFarlane; Sauer, Kenneth; Yachandra, Vittal K.

    2014-01-01

    The oxygen-evolving complex of photosystem II (PS II) in green plants and algae contains a cluster of four Mn atoms in the active site, which catalyzes the photoinduced oxidation of water to dioxygen. Along with Mn, calcium and chloride ions are necessary cofactors for proper functioning of the complex. The current study using polarized Sr EXAFS on oriented Sr-reactivated samples shows that Fourier peak II, which fits best to Mn at 3.5 Å rather than lighter atoms (C, N, O, or Cl), is dichroic, with a larger magnitude at 10° (angle between the PS II membrane normal and the X-ray electric field vector) and a smaller magnitude at 80°. Analysis of the dichroism of the Sr EXAFS yields a lower and upper limit of 0° and 23° for the average angle between the Sr–Mn vectors and the membrane normal and an isotropic coordination number (number of Mn neighbors to Sr) of 1 or 2 for these layered PS II samples. The results confirm the contention that Ca (Sr) is proximal to the Mn cluster and lead to refined working models of the heteronuclear Mn4Ca cluster of the oxygen-evolving complex in PS II. PMID:15491134

  12. 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.

  13. 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.

  14. Dimensionless, Scale Invariant, Edge Weight Metric for the Study of Complex Structural Networks

    PubMed Central

    Colon-Perez, Luis M.; Spindler, Caitlin; Goicochea, Shelby; Triplett, William; Parekh, Mansi; Montie, Eric; Carney, Paul R.; Price, Catherine; Mareci, Thomas H.

    2015-01-01

    High spatial and angular resolution diffusion weighted imaging (DWI) with network analysis provides a unique framework for the study of brain structure in vivo. DWI-derived brain connectivity patterns are best characterized with graph theory using an edge weight to quantify the strength of white matter connections between gray matter nodes. Here a dimensionless, scale-invariant edge weight is introduced to measure node connectivity. This edge weight metric provides reasonable and consistent values over any size scale (e.g. rodents to humans) used to quantify the strength of connection. Firstly, simulations were used to assess the effects of tractography seed point density and random errors in the estimated fiber orientations; with sufficient signal-to-noise ratio (SNR), edge weight estimates improve as the seed density increases. Secondly to evaluate the application of the edge weight in the human brain, ten repeated measures of DWI in the same healthy human subject were analyzed. Mean edge weight values within the cingulum and corpus callosum were consistent and showed low variability. Thirdly, using excised rat brains to study the effects of spatial resolution, the weight of edges connecting major structures in the temporal lobe were used to characterize connectivity in this local network. The results indicate that with adequate resolution and SNR, connections between network nodes are characterized well by this edge weight metric. Therefore this new dimensionless, scale-invariant edge weight metric provides a robust measure of network connectivity that can be applied in any size regime. PMID:26173147

  15. Dimensionless, Scale Invariant, Edge Weight Metric for the Study of Complex Structural Networks.

    PubMed

    Colon-Perez, Luis M; Spindler, Caitlin; Goicochea, Shelby; Triplett, William; Parekh, Mansi; Montie, Eric; Carney, Paul R; Price, Catherine; Mareci, Thomas H

    2015-01-01

    High spatial and angular resolution diffusion weighted imaging (DWI) with network analysis provides a unique framework for the study of brain structure in vivo. DWI-derived brain connectivity patterns are best characterized with graph theory using an edge weight to quantify the strength of white matter connections between gray matter nodes. Here a dimensionless, scale-invariant edge weight is introduced to measure node connectivity. This edge weight metric provides reasonable and consistent values over any size scale (e.g. rodents to humans) used to quantify the strength of connection. Firstly, simulations were used to assess the effects of tractography seed point density and random errors in the estimated fiber orientations; with sufficient signal-to-noise ratio (SNR), edge weight estimates improve as the seed density increases. Secondly to evaluate the application of the edge weight in the human brain, ten repeated measures of DWI in the same healthy human subject were analyzed. Mean edge weight values within the cingulum and corpus callosum were consistent and showed low variability. Thirdly, using excised rat brains to study the effects of spatial resolution, the weight of edges connecting major structures in the temporal lobe were used to characterize connectivity in this local network. The results indicate that with adequate resolution and SNR, connections between network nodes are characterized well by this edge weight metric. Therefore this new dimensionless, scale-invariant edge weight metric provides a robust measure of network connectivity that can be applied in any size regime.

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

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

    PubMed

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

    2016-03-07

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

  18. 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

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

    PubMed

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

    2016-01-01

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

  20. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

    DOE PAGES

    Kortright, Jeffrey Barrett; Sun, Jing; Spencer, Ryan K.; ...

    2016-12-14

    The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc 12-b-pNte 21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODTmore » corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.« less

  1. 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.

  2. 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).

  3. Edge currents in frustrated Josephson junction ladders

    NASA Astrophysics Data System (ADS)

    Marques, A. M.; Santos, F. D. R.; Dias, R. G.

    2016-09-01

    We present a numerical study of quasi-1D frustrated Josephson junction ladders with diagonal couplings and open boundary conditions, in the large capacitance limit. We derive a correspondence between the energy of this Josephson junction ladder and the expectation value of the Hamiltonian of an analogous tight-binding model, and show how the overall superconducting state of the chain is equivalent to the minimum energy state of the tight-binding model in the subspace of one-particle states with uniform density. To satisfy the constraint of uniform density, the superconducting state of the ladder is written as a linear combination of the allowed k-states of the tight-binding model with open boundaries. Above a critical value of the parameter t (ratio between the intra-rung and inter-rung Josephson couplings) the ladder spontaneously develops currents at the edges, which spread to the bulk as t is increased until complete coverage is reached. Above a certain value of t, which varies with ladder size (t = 1 for an infinite-sized ladder), the edge currents are destroyed. The value t = 1 corresponds, in the tight-binding model, to the opening of a gap between two bands. We argue that the disappearance of the edge currents with this gap opening is not coincidental, and that this points to a topological origin for these edge current states.

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

    PubMed

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

    2013-08-15

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

  5. Numerical analysis of the reverse blocking enhancement in High-K passivation AlGaN/GaN Schottky barrier diodes with gated edge termination

    NASA Astrophysics Data System (ADS)

    Bai, Zhiyuan; Du, Jiangfeng; Xin, Qi; Li, Ruonan; Yu, Qi

    2018-02-01

    We conducted a numerical analysis on high-K dielectric passivated AlGaN/GaN Schottky barrier diodes (HPG-SBDs) with a gated edge termination (GET). The reverse blocking characteristics were significantly enhanced without the stimulation of any parasitic effect by varying the dielectric thickness dge under the GET, thickness TP, and dielectric constant εr of the high-K passivation layer. The leakage current was reduced by increasing εr and decreasing dge. The breakdown voltage of the device was enhanced by increasing εr and TP. The highest breakdown voltage of 970 V and the lowest leakage current of 0.5 nA/mm were achieved under the conditions of εr = 80, TP = 800 nm, and dge = 10 nm. C-V simulation revealed that the HPG-SBDs induced no parasitic capacitance by comparing the integrated charges of the devices with different high-K dielectrics and different dge.

  6. Effects of Cutting Edge Microgeometry on Residual Stress in Orthogonal Cutting of Inconel 718 by FEM.

    PubMed

    Shen, Qi; Liu, Zhanqiang; Hua, Yang; Zhao, Jinfu; Lv, Woyun; Mohsan, Aziz Ul Hassan

    2018-06-14

    Service performance of components such as fatigue life are dramatically influenced by the machined surface and subsurface residual stresses. This paper aims at achieving a better understanding of the influence of cutting edge microgeometry on machined surface residual stresses during orthogonal dry cutting of Inconel 718. Numerical and experimental investigations have been conducted in this research. The cutting edge microgeometry factors of average cutting edge radius S¯, form-factor K , and chamfer were investigated. An increasing trend for the magnitudes of both tensile and compressive residual stresses was observed by using larger S¯ or introducing a chamfer on the cutting edges. The ploughing depth has been predicted based on the stagnation zone. The increase of ploughing depth means that more material was ironed on the workpiece subsurface, which resulted in an increase in the compressive residual stress. The thermal loads were leading factors that affected the surface tensile residual stress. For the unsymmetrical honed cutting edge with K = 2, the friction between tool and workpiece and tensile residual stress tended to be high, while for the unsymmetrical honed cutting edge with K = 0.5, the high ploughing depth led to a higher compressive residual stress. This paper provides guidance for regulating machine-induced residual stress by edge preparation.

  7. 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.

  8. 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.

  9. The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

    NASA Astrophysics Data System (ADS)

    Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

    2007-09-01

    The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron

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

    NASA Astrophysics Data System (ADS)

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

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

  11. A study of interply layer effects on the free-edge stress field of angleplied laminates

    NASA Technical Reports Server (NTRS)

    Murthy, P. L. N.; Chamis, C. C.

    1984-01-01

    The general-purpose finite-element program MSC/NASTRAN is used to study the interply layer effects on the free-edge stress field of symmetric angleplied laminates subjected to uniform tensile stress. The free-edge region is modeled as a separate substructure (superelement) which enables easy mesh refinement and provides the flexibility to move the superelement along the edge. The results indicate that the interply layer reduces the stress intensity significantly at the free edge. Another important observation of the study is that the failures observed near free edges of these types of laminates could have been caused by the interlaminar shear stresses.

  12. A superior edge preserving filter with a systematic analysis

    NASA Technical Reports Server (NTRS)

    Holladay, Kenneth W.; Rickman, Doug

    1991-01-01

    A new, adaptive, edge preserving filter for use in image processing is presented. It had superior performance when compared to other filters. Termed the contiguous K-average, it aggregates pixels by examining all pixels contiguous to an existing cluster and adding the pixel closest to the mean of the existing cluster. The process is iterated until K pixels were accumulated. Rather than simply compare the visual results of processing with this operator to other filters, some approaches were developed which allow quantitative evaluation of how well and filter performs. Particular attention is given to the standard deviation of noise within a feature and the stability of imagery under iterative processing. Demonstrations illustrate the performance of several filters to discriminate against noise and retain edges, the effect of filtering as a preprocessing step, and the utility of the contiguous K-average filter when used with remote sensing data.

  13. Energy-discrimination X-ray computed tomography system utilizing a silicon-PIN detector and its application to 2.0-keV-width K-edge imaging

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

    Demonstration of narrow-energy-width computed tomography (CT) was carried out by means of energy-discrimination. An X-ray CT system is of a first-generation type and consists of an X-ray generator, a turntable, a translation stage, a two-stage controller, a silicon-PIN detector system with amplifiers, a multi-channel analyzer (MCA), a counter card (CC), and a personal computer (PC). CT is accomplished by repeating the translation and the rotation of an object, and projection curves of the object are obtained by the translation of the moving object. Both photon-energy level and energy width are determined by the MCA, and the pulses of the discriminated event signal from the MCA are counted by CC in conjunction with PC. The maximum count rate was approximately 300 cps (counts per second) with energy widths of 2.0 keV, and energy-discrimination CT was carried out with a photon-energy resolution of 0.15 keV. To perform iodine K-edge CT, X-ray photons with an energy range from 33.2 to 35.2 keV were used. Next, to carry out cerium K-edge CT, an energy range from 40.3 to 42.3 keV was selected.

  14. Synchrotron speciation data for zero-valent iron nanoparticles

    EPA Pesticide Factsheets

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

  15. Orbital Ordering Transition in La_4Ru_2O_10 probed by O K-edge X-ray Absorption

    NASA Astrophysics Data System (ADS)

    Denlinger, J. D.; Rossnagel, Kai; Allen, J. W.; Khalifah, P.; Mandrus, D.; Cava, R. J.

    2004-03-01

    The layered ruthenate compound La_4Ru_2O_10 undergoes a first order monoclinic-to-triclinic structural phase transition at 160 K. An accompanying loss of the Ru local moment gives evidence for a full orbital ordering transition in which the Ru d_yz orbitals become completely unoccupied in the low temperature phase.(P. Khalifah et al.), Science 297, 2237 (2002). Via hybridization of Ru t_2g and O 2p orbitals this temperature-dependent Ru orbital ordering can be indirectly probed using polarized O K-edge x-ray absorption spectroscopy (XAS). O 1s core-level energy shifts allow O site-specific separation of Ru t_2g hybridizations. Identification of O sites is accomplished using polarized XAS angular dependence as well as by O 2p valence PDOS obtained from site-selective soft x-ray emission. Distinct XAS energy and intensity changes are observed upon cooling through the phase transition and are rationalized within the framework of the complete orbital ordering scenario. Supported by the U.S. NSF at U. Mich. (DMR-03-02825) and by the DOE at the Advanced Light Source (DE-AC03-76SF00098).

  16. 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

  17. Living on the edge: roads and edge effects on small mammal populations.

    PubMed

    Fuentes-Montemayor, Elisa; Cuarón, Alfredo D; Vázquez-Domínguez, Ella; Benítez-Malvido, Julieta; Valenzuela-Galván, David; Andresen, Ellen

    2009-07-01

    1. Roads may affect wildlife populations through habitat loss and disturbances, as they create an abrupt linear edge, increasing the proportion of edge exposed to a different habitat. Three types of edge effects have been recognized: abiotic, direct biotic, and indirect biotic. 2. We explored the direct biotic edge effects of 3- to 4-m wide roads, and also a previously unrecognized type of edge effect: social. We live-trapped two threatened endemic rodents from Cozumel Island (Oryzomys couesi cozumelae and Reithrodontomys spectabilis) in 16 plots delimited by roads on two sides, to compare edge effects between two adjacent edges (corners), single-edge and interior forest, on life history and social variables. 3. No significant edge effects were observed on the life-history variables, with the exception of differences in body condition between males and females of O. c. cozumelae near edges. Both species showed significant and contrasting effects on their social variables. 4. O. c. cozumelae was distributed according to its age and sex: the proportion of adults and males was higher in interior than near edges, while juveniles and females were more abundant near edges. More nonreproductive females were present in corners than in single-edge and interior, while the opposite distribution was observed for nonreproductive males. 5. The distribution of R. spectabilis was related to its age and reproductive condition, but not to its sex. The proportion of adults was significantly higher in corners, while juveniles were only caught in single-edge and interior quadrants. The proportion of reproductive individuals was higher in edge than interior quadrants, while reproductive females were only present in edge quadrants. 6. We found significant differences between the quadrants with the greatest edge exposure in comparison with other quadrants. The social edge effects we identified complement the typology of edge effects recognized in ecological literature. Our study provides

  18. Wavelet-based edge correlation incorporated iterative reconstruction for undersampled MRI.

    PubMed

    Hu, Changwei; Qu, Xiaobo; Guo, Di; Bao, Lijun; Chen, Zhong

    2011-09-01

    Undersampling k-space is an effective way to decrease acquisition time for MRI. However, aliasing artifacts introduced by undersampling may blur the edges of magnetic resonance images, which often contain important information for clinical diagnosis. Moreover, k-space data is often contaminated by the noise signals of unknown intensity. To better preserve the edge features while suppressing the aliasing artifacts and noises, we present a new wavelet-based algorithm for undersampled MRI reconstruction. The algorithm solves the image reconstruction as a standard optimization problem including a ℓ(2) data fidelity term and ℓ(1) sparsity regularization term. Rather than manually setting the regularization parameter for the ℓ(1) term, which is directly related to the threshold, an automatic estimated threshold adaptive to noise intensity is introduced in our proposed algorithm. In addition, a prior matrix based on edge correlation in wavelet domain is incorporated into the regularization term. Compared with nonlinear conjugate gradient descent algorithm, iterative shrinkage/thresholding algorithm, fast iterative soft-thresholding algorithm and the iterative thresholding algorithm using exponentially decreasing threshold, the proposed algorithm yields reconstructions with better edge recovery and noise suppression. Copyright © 2011 Elsevier Inc. All rights reserved.

  19. 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.

  20. Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

    NASA Astrophysics Data System (ADS)

    Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

    2009-04-01

    Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of

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

    PubMed Central

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

    2016-01-01

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

  2. Experimental investigation of edge hardening and edge cracking sensitivity of burr-free parts

    NASA Astrophysics Data System (ADS)

    Senn, Sergei; Liewald, Mathias

    2018-05-01

    This experimental study is focused on characterisation of edge hardening of sheet metal and remaining formability of differently prepared cutted edges. Edge cracking sensitivity of counter cutted, shear cutted, recutted and water-jet cutted components are compared and evaluated. Subsequently, edge hardening and hole expansion ratio were correlated for material HC420 LA with sheet thickness of t = 2 mm. As other studies show, the cutting edge surface quality influences the hole expansion ratio: a high clear cut surface increases formability of cutting edges, whereas micro cracks and rough surfaces result into a large fracture surface, which impact remaining formability noticeably. Thus, cutting edges with lower edge hardening behaviour in conjunction with a higher clear cut surface exhibit higher hole expansion ratios. Counter cutting and the recutting do show a similar effect on edge hardening. Using the hole expansion test, it was possible to prove that counter cutted components show a significantly lower edge cracking sensitivity in comparison to conventionally shear cutted components. The hole expansion ratio of counter cutted specimens looks balanced and is comparable to the hole expansion ratio measured from specimens with recutted or water jet cutted edges. The significant difference of the investigated cutting processes is characterized by size of clear cutting area. This area of recutted edges emerges larger than the area of counter cutted specimens, which evidently leads to an increased hole expansion ratio of recutted specimens compared to conventionally shear cutted ones. However, it is important to note that the hole expansion ratio of counter cutted and recutted specimens appear fairly balanced, but counter cutted samples indeed can be produced burr-free. Using counter cutting technology, it is possible to produce burr free surfaces with high edge formability.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  5. Fe K-Edge X-ray absorption near-edge spectroscopy (XANES) and X-ray diffraction (XRD) analyses of LiFePO4 and its base materials

    NASA Astrophysics Data System (ADS)

    Latif, C.; Negara, V. S. I.; Wongtepa, W.; Thamatkeng, P.; Zainuri, M.; Pratapa, S.

    2018-03-01

    XANES analysis has been performed with the aim of knowing the Fe oxidation state in a synthesized LiFePO4 and its base materials. XANES measurements were performed at SLRI on energy around Fe K-edge. An XRD analysis has also been performed with the aim of knowing the phase composition, lattice parameters and crystallite size of the LiFePO4 as well as the base materials. From the XRD analysis, it was found that the dominating phase in the iron sand sample was Fe3O4 and the only phase found after calcination was LiFePO4. The latter phase exhibited crystallite size of 100 nm and lattice parameters a = 10.169916 Å, b = 5.919674 Å, c = 4.627893 Å. Qualitative analysis of XANES data revealed that the oxidation number of Fe in the sample before calcination was greater than that after calcination and Fe in the natural iron sand, indicated by the E0 values of 7129.2 eV, 7120.6 eV and 7124.4 eV respectively.

  6. 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

  7. 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.

  8. Scanned gate microscopy of inter-edge channel scattering in the quantum Hall regime

    NASA Astrophysics Data System (ADS)

    Woodside, Michael T.; Vale, Chris; McEuen, Paul L.; Kadow, C.; Maranowski, K. D.; Gossard, A. C.

    2000-03-01

    Novel scanned probe techniques have recently been used to study in detail the microscopic properties of 2D electron gases in the quantum Hall regime [1]. We report local measurements of the scattering between edge states in a quantum Hall conductor with non-equilibrium edge state populations. Using an atomic force microscope (AFM) tip as a local gate to perturb the edge states, we find that the scattering is dominated by individual, microscopic scattering sites, which we directly image and characterise. The dependence of the scattering on the AFM tip voltage reveals that it involves tunneling both through quasi-bound impurity states and through disorder-induced weak links between the edge states. [1] S. H. Tessmer et al., Nature 392, 51 (1998); K. L. McCormick et al., Phys. Rev. B 59, 4654 (1999); A. Yacoby et al., Solid State Comm. 111, 1 (1999).

  9. Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce2(C8H8)3 and Ce(C8H8)2

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

    Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W.

    2009-02-02

    New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolatedmore » f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a"triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules.« less

  10. Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II

    PubMed Central

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

    2016-01-01

    The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis. PMID:28044099

  11. Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4CaO 5 cluster in the oxygen-evolving complex of photosystem II

    DOE PAGES

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

    2016-05-09

    The Mn 4CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in themore » S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

  12. Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study.

    PubMed

    Cui, Jinli; Jing, Chuanyong; Che, Dongsheng; Zhang, Jianfeng; Duan, Shuxuan

    2015-06-01

    Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5mg/L Ca(ClO)2. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water. Copyright © 2015. Published by Elsevier B.V.

  13. Computational Study of Porous Treatment for Altering Flap Side-Edge Flowfield

    NASA Technical Reports Server (NTRS)

    Choudhari, Meelan; Khorrami, Mehdi R.

    2003-01-01

    Reynolds-averaged Navier-Stokes calculations are used to investigate porous side-edge treatment as a passive means for flap noise reduction. Steady-state simulations are used to infer effects of the treatment on acoustically relevant features of the mean flow near the flap side edge. Application of the porous treatment over a miniscule fraction of the wetted flap area (scaling with the flap thickness) results in significantly weaker side-edge vortex structures via modification of the vortex initiation and roll-up processes. At high flap deflections, the region of axial flow reversal associated with the breakdown of the side-edge vortex is also eliminated, indicating an absence of vortex bursting in the presence of the treatment. Potential ramifications of the mean-flow modifications for flap-noise reduction are examined in the light of lessons learned from recent studies on flap noise. Computations confirm that any noise reduction benefit via the porous treatment would be achieved without compromising the aerodynamic effectiveness of the flap. Results of the parameter study contribute additional insight into the measured data from the 7x10 wind tunnel at NASA Ames and provide preliminary guidance for specifying optimal treatment characteristics in terms of treatment location, spatial extent, and flow resistance of the porous skin.

  14. 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.

  15. High Velocity Linear Induction Launcher with Exit-Edge Compensation for Testing of Aerospace Components

    NASA Technical Reports Server (NTRS)

    Kuznetsov, Stephen; Marriott, Darin

    2008-01-01

    Advances in ultra high speed linear induction electromagnetic launchers over the past decade have focused on magnetic compensation of the exit and entry-edge transient flux wave to produce efficient and compact linear electric machinery. The paper discusses two approaches to edge compensation in long-stator induction catapults with typical end speeds of 150 to 1,500 m/s. In classical linear induction machines, the exit-edge effect is manifest as two auxiliary traveling waves that produce a magnetic drag on the projectile and a loss of magnetic flux over the main surface of the machine. In the new design for the Stator Compensated Induction Machine (SCIM) high velocity launcher, the exit-edge effect is nulled by a dual wavelength machine or alternately the airgap flux is peaked at a location prior to the exit edge. A four (4) stage LIM catapult is presently being constructed for 180 m/s end speed operation using double-sided longitudinal flux machines. Advanced exit and entry edge compensation is being used to maximize system efficiency, and minimize stray heating of the reaction armature. Each stage will output approximately 60 kN of force and produce over 500 G s of acceleration on the armature. The advantage of this design is there is no ablation to the projectile and no sliding contacts, allowing repeated firing of the launcher without maintenance of any sort. The paper shows results of a parametric study for 500 m/s and 1,500 m/s linear induction launchers incorporating two of the latest compensation techniques for an air-core stator primary and an iron-core primary winding. Typical thrust densities for these machines are in the range of 150 kN/sq.m. to 225 kN/sq.m. and these compete favorably with permanent magnet linear synchronous machines. The operational advantages of the high speed SCIM launcher are shown by eliminating the need for pole-angle position sensors as would be required by synchronous systems. The stator power factor is also improved.

  16. Unveiling the complex network of interactions in Ionic Liquids: a combined EXAFS and Molecular Dynamics approach

    NASA Astrophysics Data System (ADS)

    Serva, A.; Migliorati, V.; Lapi, A.; D'Angelo, P.

    2016-05-01

    The structural properties of geminal dicationic ionic liquids ([Cn (mim)2]Br2)/water mixtures have been investigated by means of extended X-ray absorption fine structure (EXAFS) spectroscopy and Molecular Dynamics (MD) simulations. This synergic approach allowed us to assess the reliability of the MD results and to provide accurate structural information about the first coordination shell of the Br- ion. We found that the local environment around the anion changes as a function of the water concentration, while it is the same independently from the length of the bridge-alkyl chain. Moreover, as regards the long-range structural organization, no tail-tail aggregation occurs with increasing alkyl chain length.

  17. Fermi edge singularities in the mesoscopic regime: Photoabsorption spectra

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  18. Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Kirpichtchikova, Tatiana A.; Manceau, Alain; Spadini, Lorenzo; Panfili, Fré; dé; ric; Marcus, Matthew A.; Jacquet, Thierry

    2006-05-01

    Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S, S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si 4(Mg 1.65Zn 1.35)O 10(OH) 2 · nH 2O), willemite (Zn 2SiO 4), and gahnite (ZnAl 2O 4), in proportions of ˜30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting

  19. Edge modulation of electronics and transport properties of cliff-edge phosphorene nanoribbons

    NASA Astrophysics Data System (ADS)

    Guo, Caixia; Wang, Tianxing; Xia, Congxin; Liu, Yufang

    2017-12-01

    Based on the first-principles calculations, we study the electronic structures and transport properties of cliff-like edge phosphorene nanoribbons (CPNRs), considering different types of edge passivation. The band structures of bare CPNRs possess the metallic features; while hydrogen (H), fluorine (F), chlorine (Cl) and oxygen (O) atoms-passivated CPNRs are semiconductor materials, and the band gap values monotonically decrease when the ribbon width increases. Moreover, the H and F-passivated CPNRs exhibit the direct band gap characteristics, while the Cl and O-passivated cases show the features of indirect band gap. In addition, the edge passivated CPNRs are more energetically stable than bare edge case. Meanwhile, our results also show that the transport properties of the CPNRs can be obviously influenced by the different edge passivation.

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

    PubMed

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

    2003-09-23

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

  1. 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

  2. Multiple rare-earth ion environments in amorphous (Gd2O3 ) 0.230(P2O5) 0.770 revealed by gadolinium K -edge anomalous x-ray scattering

    NASA Astrophysics Data System (ADS)

    Cole, Jacqueline M.; Cramer, Alisha J.; Shastri, Sarvjit D.; Mukaddem, Karim T.; Newport, Robert J.

    2018-04-01

    A Gd K -edge anomalous x-ray scattering (AXS) study is performed on the rare-earth (R ) phosphate glass, (Gd2O3 ) 0.230(P2O5) 0.770 , in order to determine Gd ⋯Gd separations in its local structure. The minimum rare-earth separation is of particular interest given that the optical properties of these glasses can quench when rare-earth ions become too close to each other. To this end, a weak Gd ⋯Gd pairwise correlation is located at 4.2 (1 )Å , which is representative of a metaphosphate R ⋯R separation. More intense first-neighbor Gd ⋯Gd pairwise correlations are found at the larger radial distributions, 4.8(1), 5.1(1), and 5.4 (1 )Å . These reflect a mixed ultraphosphate and metaphosphate structural character, respectively. A second-neighbor Gd ⋯Gd pairwise correlation lies at 6.6 (1 )Å which is indicative of metaphosphate structures. Meta- and ultraphosphate classifications are made by comparing the R ⋯R separations against those of rare-earth phosphate crystal structures, R (PO3) 3 and R P5O14 , respectively, or difference pair-distribution function (Δ PDF ) features determined on similar glasses using difference neutron-scattering methods. The local structure of this glass is therefore found to display multiple rare-earth ion environments, presumably because its composition lies between these two stoichiometric formulae. These Gd ⋯Gd separations are well-resolved in Δ PDFs that represent the AXS signal. Indeed, the spatial resolution is so good that it also enables the identification of R ⋯X (X =R , P, O) pairwise correlations up to r ˜9 Å ; their average separations lie at r ˜7.1 (1 ) , 7.6(1), 7.9(1), 8.4(1), and 8.7 (1 )Å . This is a report of a Gd K -edge AXS study on an amorphous material. Its demonstrated ability to characterize the local structure of a glass up to such a long range of r heralds exciting prospects for AXS studies on other ternary noncrystalline materials. However, the technical

  3. Multi-frame acquisition scheme for efficient energy-dispersive X-ray magnetic circular dichroism in pulsed high magnetic fields at the Fe K-edge

    PubMed Central

    Strohm, Cornelius; Perrin, Florian; Dominguez, Marie-Christine; Headspith, Jon; van der Linden, Peter; Mathon, Olivier

    2011-01-01

    Using a fast silicon strip detector, a multi-frame acquisition scheme was implemented to perform energy-dispersive X-ray magnetic circular dichroism at the iron K-edge in pulsed high magnetic fields. The acquisition scheme makes use of the entire field pulse. The quality of the signal obtained from samples of ferrimagnetic erbium iron garnet allows for quantitative evaluation of the signal amplitude. Below the compensation point, two successive field-induced phase transitions and the reversal of the net magnetization of the iron sublattices in the intermediate phase were observed. PMID:21335909

  4. Giant edge spin accumulation in a symmetric quantum well with two subbands

    NASA Astrophysics Data System (ADS)

    Khaetskii, Alexander; Egues, J. Carlos

    We have studied the edge spin accumulation due to an electric current in a high mobility two-dimensional electron gas formed in a symmetric well with two subbands. This study is strongly motivated by recent experiments which demonstrated the spin accumulation near the edges of a symmetric bilayer GaAs structure in contrast to no effect in a single-layer configuration. The intrinsic mechanism of the spin-orbit interaction we consider arises from the coupling between two subband states of opposite parities. Following the method developed in, we show that the presence of a gap in the system (i.e., the energy separation between the two subband bottoms) changes drastically the picture of the edge spin accumulation. We obtain a parametrically large magnitude of the edge spin density for a two-subband well as compared to the usual single-subband structure, and show that by changing the gap from zero up to 1 ÷2 K, the magnitude of the effect changes by three orders of magnitude. It opens up the possibility for the design of new interesting spintronic devices. We acknowledge financial support from FAPESP.

  5. Controlled formation of closed-edge nanopores in graphene

    NASA Astrophysics Data System (ADS)

    He, Kuang; Robertson, Alex W.; Gong, Chuncheng; Allen, Christopher S.; Xu, Qiang; Zandbergen, Henny; Grossman, Jeffrey C.; Kirkland, Angus I.; Warner, Jamie H.

    2015-07-01

    Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport.Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport. Electronic supplementary information (ESI) available: Low magnification images, image processing techniques employed, modelling and simulation of closed edge nanoribbon, comprehensive AC-TEM dataset, and supporting analysis. See DOI: 10.1039/c5nr02277k

  6. Identification of column edges of DNA fragments by using K-means clustering and mean algorithm on lane histograms of DNA agarose gel electrophoresis images

    NASA Astrophysics Data System (ADS)

    Turan, Muhammed K.; Sehirli, Eftal; Elen, Abdullah; Karas, Ismail R.

    2015-07-01

    Gel electrophoresis (GE) is one of the most used method to separate DNA, RNA, protein molecules according to size, weight and quantity parameters in many areas such as genetics, molecular biology, biochemistry, microbiology. The main way to separate each molecule is to find borders of each molecule fragment. This paper presents a software application that show columns edges of DNA fragments in 3 steps. In the first step the application obtains lane histograms of agarose gel electrophoresis images by doing projection based on x-axis. In the second step, it utilizes k-means clustering algorithm to classify point values of lane histogram such as left side values, right side values and undesired values. In the third step, column edges of DNA fragments is shown by using mean algorithm and mathematical processes to separate DNA fragments from the background in a fully automated way. In addition to this, the application presents locations of DNA fragments and how many DNA fragments exist on images captured by a scientific camera.

  7. In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS (Extended X-Ray Absorption Fine Structure).

    DTIC Science & Technology

    1988-01-28

    EXAFS is the inverse transform of the two peaks in the RSF using a filtering a12 function to isolate the range between I and 4A. Both the frequency...backscattering of different neighbors. This inverse transform contains only one frequency and its envelope of intensity is the backscattering amplitude function...and the inverse transform of the RSF using a fourier filter between 1 and 4A (Solid line). Insert: Radial Structure Function (RSF) analyzed between

  8. The Erdős-Rothschild problem on edge-colourings with forbidden monochromatic cliques

    NASA Astrophysics Data System (ADS)

    Pikhurko, Oleg; Staden, Katherine; Yilma, Zelealem B.

    2017-09-01

    Let $\\mathbf{k} := (k_1,\\dots,k_s)$ be a sequence of natural numbers. For a graph $G$, let $F(G;\\mathbf{k})$ denote the number of colourings of the edges of $G$ with colours $1,\\dots,s$ such that, for every $c \\in \\{1,\\dots,s\\}$, the edges of colour $c$ contain no clique of order $k_c$. Write $F(n;\\mathbf{k})$ to denote the maximum of $F(G;\\mathbf{k})$ over all graphs $G$ on $n$ vertices. This problem was first considered by Erd\\H{o}s and Rothschild in 1974, but it has been solved only for a very small number of non-trivial cases. We prove that, for every $\\mathbf{k}$ and $n$, there is a complete multipartite graph $G$ on $n$ vertices with $F(G;\\mathbf{k}) = F(n;\\mathbf{k})$. Also, for every $\\mathbf{k}$ we construct a finite optimisation problem whose maximum is equal to the limit of $\\log_2 F(n;\\mathbf{k})/{n\\choose 2}$ as $n$ tends to infinity. Our final result is a stability theorem for complete multipartite graphs $G$, describing the asymptotic structure of such $G$ with $F(G;\\mathbf{k}) = F(n;\\mathbf{k}) \\cdot 2^{o(n^2)}$ in terms of solutions to the optimisation problem.

  9. Clinical evaluation of a 2K x 2K workstation for primary diagnosis in pediatric radiology

    NASA Astrophysics Data System (ADS)

    Razavi, Mahmood; Sayre, James W.; Simons, Margaret A.; Hamedaninia, Azar; Boechat, Maria I.; Hall, Theodore R.; Kangarloo, Hooshang; Taira, Ricky K.; Chuang, Keh-Shih; Kashifian, Payam

    1991-07-01

    Preliminary results of a large-scale ROC study evaluating the diagnostic performance of digital hardcopy film and 2K X 2K softcopy display for pediatric chest radiographs are presented. The pediatric disease categories studied were pneumothorax, linear atelectasis, air bronchograms, and interstitial disease. Digital images were obtained directly from a computed radiography system. Results from the readings of 239 chest radiographs by 4 radiologists show no significant difference between viewing images on film and softcopy display for the disease categories pneumothorax and air bronchograms. A slight performance edge for softcopy was seen for the disease categories of interstitial disease and linear atelectasis.

  10. Structure and spectroscopic study of aqueous Fe(III)-As(V) complexes using UV-Vis, XAS and DFT-TDDFT.

    PubMed

    Chai, Liyuan; Yang, Jinqin; Zhang, Ning; Wu, Pin-Jiun; Li, Qingzhu; Wang, Qingwei; Liu, Hui; Yi, Haibo

    2017-09-01

    Aqueous complexes between ferric (Fe(III)) and arsenate (As(V)) are indispensable for understanding the mobility of arsenic (As) in Fe(III)-As(V)-rich systems. In this study, aqueous Fe(III)-As(V) complexes, FeH 2 AsO 4 2+ and FeHAsO 4 + , were postulated based on the qualitative analysis of UV-Vis spectra in both Fe(III)-As(V)-HClO 4 and Fe(III)-As(V)-H 2 SO 4 systems. Subsequently, monodentate structures were evidenced by Fe K-edge EXAFS and modeled as [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + by DFT. The feature band at ∼280 nm was verified as electron excitation chiefly from Fe-As-bridged O atoms to d-orbital of Fe in [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + . The structural and spectral information of Fe(III)-As(V) complexes will enable future speciation analysis in Fe(III)-As(V)-rich system. Copyright © 2017. Published by Elsevier Ltd.

  11. An evaluation of edge effects in nutritional accessibility and availability measures: a simulation study

    PubMed Central

    2010-01-01

    Background This paper addresses the statistical use of accessibility and availability indices and the effect of study boundaries on these measures. The measures are evaluated via an extensive simulation based on cluster models for local outlet density. We define outlet to mean either food retail store (convenience store, supermarket, gas station) or restaurant (limited service or full service restaurants). We designed a simulation whereby a cluster outlet model is assumed in a large study window and an internal subset of that window is constructed. We performed simulations on various criteria including one scenario representing an urban area with 2000 outlets as well as a non-urban area simulated with only 300 outlets. A comparison is made between estimates obtained with the full study area and estimates using only the subset area. This allows the study of the effect of edge censoring on accessibility measures. Results The results suggest that considerable bias is found at the edges of study regions in particular for accessibility measures. Edge effects are smaller for availability measures (when not smoothed) and also for short range accessibility Conclusions It is recommended that any study utilizing these measures should correct for edge effects. The use of edge correction via guard areas is recommended and the avoidance of large range distance-based accessibility measures is also proposed. PMID:20663199

  12. 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

  13. Airfoil noise reductions through leading edge serrations

    NASA Astrophysics Data System (ADS)

    Narayanan, S.; Chaitanya, P.; Haeri, S.; Joseph, P.; Kim, J. W.; Polacsek, C.

    2015-02-01

    This paper provides an experimental investigation into the use of leading edge (LE) serrations as a means of reducing the broadband noise generated due to the interaction between the aerofoil's LE and impinging turbulence. Experiments are performed on a flat plate in an open jet wind tunnel. Grids are used to generate isotropic homogeneous turbulence. The leading edge serrations are in the form of sinusoidal profiles of wavelengths, λ, and amplitudes, 2h. The frequency and amplitude characteristics are studied in detail in order to understand the effect of LE serrations on noise reduction characteristics and are compared with straight edge baseline flat plates. Noise reductions are found to be insignificant at low frequencies but significant in the mid frequency range (500 Hz-8 kHz) for all the cases studied. The flat plate results are also compared to the noise reductions obtained on a serrated NACA-65 aerofoil with the same serration profile. Noise reductions are found to be significantly higher for the flat plates with a maximum noise reduction of around 9 dB compared with about 7 dB for the aerofoil. In general, it is observed that the sound power reduction level (ΔPWL) is sensitive to the amplitude, 2h of the LE serrations but less sensitive to the serration wavelength, λ. Thus, this paper sufficiently demonstrates that the LE amplitude acts as a key parameter for enhancing the noise reduction levels in flat plates and aerofoils.

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

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

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

    2017-01-01

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

  15. K-shell photoabsorption coefficients of O2, CO2, CO, and N2O

    NASA Technical Reports Server (NTRS)

    Barrus, D. M.; Blake, R. L.; Burek, A. J.; Chambers, K. C.; Pregenzer, A. L.

    1979-01-01

    The total photoabsorption coefficient has been measured from 500 to 600 eV around the K edge of oxygen in gases O2, CO2, CO, and N2O by means of a gold continuum source and crystal spectrometer with better than 1-eV resolution. The cross sections are dominated by discrete molecular-orbital transitions below the K-edge energy. A few Rydberg transitions were barely detectable. Broad shape resonances appear at or above the K edge. Additional broad, weak features above the K edge possibly arise from shake up. Quantitative results are given that have about 10% accuracy except on the very strong peaks. All the measured features are discussed in relation to other related measurements and theory.

  16. Combined mineralogical and EXAFS characterization of polluted sediments for the definition of technological variables and constraints

    NASA Astrophysics Data System (ADS)

    Brigatti, M. F.; Elmi, C.; Laurora, A.; Malferrari, D.; Medici, L.

    2009-04-01

    An extremely severe aspect, both from environmental and economic viewpoint, is the management of polluted sediments removed from drainage and irrigation canals. Canals, in order to retain their functionality over the time, need to have their beds, periodically cleaned from sediments there accumulating. The management of removed sediments is extremely demanding, also from an economical perspective, if these latter needs to be treated as dangerous waste materials, as stated in numerous international standards. Furthermore the disposal of such a large amount of material may introduce a significant environmental impact as well. An appealing alternative is the recovery or reuse of these materials, for example in brick and tile industry, after obviously the application of appropriate techniques and protocols that could render these latter no longer a threat for human health. The assessment of the effective potential danger for human health and ecosystem of sediments before and after treatment obviously requires both a careful chemical and mineralogical characterization and, even if not always considered in the international standards, the definition of the coordination shell of heavy metals dangerous for human health, as a function of their oxidation state and coordination (e.g. Cr and Pb), and introducing technological constraints or affecting the features of the end products. Fe is a good representative for this second category, as the features of the end product, such as color, strongly depend not only from Fe concentration but also from its oxidation state, speciation and coordination. This work will first of all provide mineralogical characterization of sediments from various sampling points of irrigation and drainage canals of Po river region in the north-eastern of Italy. Samples were investigated with various approaches including X-ray powder diffraction under non-ambient conditions, thermal analysis and EXAFS spectroscopy. Obtained results, and in particular

  17. 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.

  18. On the study of wavy leading-edge vanes to achieve low fan interaction noise

    NASA Astrophysics Data System (ADS)

    Tong, Fan; Qiao, Weiyang; Xu, Kunbo; Wang, Liangfeng; Chen, Weijie; Wang, Xunnian

    2018-04-01

    The application of wavy leading-edge vanes to reduce a single-stage axial fan noise is numerically studied. The aerodynamic and acoustic performance of the fan is numerically investigated using a hybrid unsteady Reynolds averaged Navier-Stokes (URANS)/acoustic analogy method (Goldstein equations). First, the hybrid URANS/Goldstein method is developed and successfully validated against experiment results. Next, numerical simulations are performed to investigate the noise reduction effects of the wavy leading-edge vanes. The aerodynamic and acoustic performance is assessed for a fan with vanes equipped with two different wavy leading-edge profiles and compared with the performance of conventional straight leading-edge vanes. Results indicate that a fan with wavy leading-edge vanes produces lower interaction noise than the baseline fan without a significant loss in aerodynamic performance. In fact, it is demonstrated that wavy leading-edge vanes have the potential to lead to both aerodynamic and acoustic improvements. The two different wavy leading-edge profiles are shown to successfully reduce the fan tone sound power level by 1.2 dB and 4.3 dB, respectively. Fan efficiency is also improved by about 1% with one of the tested wavy leading-edge profiles. Large eddy simulation (LES) is also performed for a simplified fan stage model to assess the effects of wavy leading-edge vanes on the broadband fan noise. Results indicate that the overall sound power level of a fan can be reduced by about 4 dB with the larger wavy leading-edge profile. Finally, the noise reduction mechanisms are investigated and analysed. It is found that the wavy leading-edge profiles can induce significant streamwise vorticity around the leading-edge protuberances and reduce pressure fluctuations (especially at locations of wavy leading-edge hills) and unsteady forces on the stator vanes. The underlying mechanism of the reduced pressure fluctuations is also discussed by examining the magnitude

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

    NASA Astrophysics Data System (ADS)

    Peacock, Caroline L.; Sherman, David M.

    2005-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  1. EX6AFS: A data acquisition system for high-speed dispersive EXAFS measurements implemented using object-oriented programming techniques

    NASA Astrophysics Data System (ADS)

    Jennings, Guy; Lee, Peter L.

    1995-02-01

    In this paper we describe the design and implementation of a computerized data-acquisition system for high-speed energy-dispersive EXAFS experiments on the X6A beamline at the National Synchrotron Light Source. The acquisition system drives the stepper motors used to move the components of the experimental setup and controls the readout of the EXAFS spectra. The system runs on a Macintosh IIfx computer and is written entirely in the object-oriented language C++. Large segments of the system are implemented by means of commercial class libraries, specifically the MacApp application framework from Apple, the Rogue Wave class library, and the Hierarchical Data Format datafile format library from the National Center for Supercomputing Applications. This reduces the amount of code that must be written and enhances reliability. The system makes use of several advanced features of C++: Multiple inheritance allows the code to be decomposed into independent software components and the use of exception handling allows the system to be much more reliable in the event of unexpected errors. Object-oriented techniques allow the program to be extended easily as new requirements develop. All sections of the program related to a particular concept are located in a small set of source files. The program will also be used as a prototype for future software development plans for the Basic Energy Science Synchrotron Radiation Center Collaborative Access Team beamlines being designed and built at the Advanced Photon Source.

  2. EXAFS characterisation of metal bonding in highly luminescent, UV stable, water-soluble and biocompatible lanthanide complexes

    NASA Astrophysics Data System (ADS)

    Kalyakina, A.; Utochnikova, V.; Trigub, A.; Zubavichus, Y.; Kuzmina, N.; Bräse, S.

    2016-05-01

    The combination of X-ray diffraction with EXAFS was employed to assess the coordination environment of lanthanide complexes in solutions. This method is based on the assumption that the local structure of lanthanide complexes in solution combines elements of the crystal structure of the complex in the solid state (single- or polycrystalline) and the elements of the local structure of a lanthanide salt, completely dissociated in the solvent (usually chlorides). The success of this approach is demonstrated with the lanthanide (III) 2,3,4,5,6-pentafluorobenzoate complexes, where the local structure in aqueous and methanol solutions were estimated. Moreover, the dissociation degree of the complexes in aqueous and methanol solutions was evaluated.

  3. 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.

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

    Yung, M. M.; Cheah, S.; Kuhn, J. N.

    The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorptionmore » near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.« less

  5. Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

    NASA Astrophysics Data System (ADS)

    Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

    2017-02-01

    X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

  6. Removal of Ca 2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn 4O 5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

    DOE PAGES

    Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; ...

    2015-05-19

    We studied Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4O 5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1') and S 2 (S 2') states, the S 2'Y Z• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mnmore » K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z• (D1-Tyr161).« less

  7. Removal of Ca(2+) from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study.

    PubMed

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

    2015-10-29

    Ca(2+)-depleted and Ca(2+)-reconstituted spinach photosystem II was studied using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca(2+) ion in the Mn4O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca(2+)-depleted S1 (S1') and S2 (S2') states, the S2'YZ(•) state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca(2+)-reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca(2+)-depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca(2+)-containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca(2+) ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca(2+) ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca(2+) removal are discussed, attributing to the Ca(2+) ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ(•) (D1-Tyr161).

  8. A multi-technique approach to assess chemical speciation of phosphate in soils

    NASA Astrophysics Data System (ADS)

    Belchior Abdala, Dalton; Rodrigues, Marcos; Herrera, Wilfrand; Pavinato, Paulo Sergio

    2017-04-01

    different P pools considered in the fractionation protocol, (ii) two synchrotron-based X-ray absorption spectroscopic techniques, XANES and EXAFS, for chemical characterization of the P forms and mineralogy of Fe-(hydr)oxides present in a sample, and (iii) Scanning Electron Microscopy and Energy-Dispersive spectroscopy, SEM/EDS, to provide complimentary information to corroborate and aid in the interpretation of our P XANES data. It was shown that the combination of techniques can assist us not only in the determination of the P chemical species present in a given material, but also to better understand the complex and dynamic processes to which P is subjected in soils. The association of spectroscopy (XANES and EXAFS) and microscopy (SEM/EDS) with wet chemistry data in this study was key to shift our understanding of the relationship between P and other soil mineral components from a macroscopic into a microscopic one. This represents a strong driving force to integrate the results of multi-analytical techniques into a more complete understanding of the systems under study. In addition, we provide a library of reference spectra for P K-edge XANES containing P sorbed to single and binary mixtures of mineral analogues intended to assist in the identification of P sorbed species commonly found in soils and sediments. Key-words: P K-edge XANES, Fe K-edge EXAFS, sequential chemical fractionation, soil phosphorus

  9. 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.

  10. Multiple rare-earth ion environments in amorphous ( G d 2 O 3 ) 0.230 ( P 2 O 5 ) 0.770 revealed by gadolinium K -edge anomalous x-ray scattering

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

    Cole, Jacqueline M.; Cramer, Alisha J.; Shastri, Sarvjit D.

    A Gd K-edge anomalous X-ray scattering (AXS) study is performed on the rare-earth (R) phosphate glass, (Gd2O3)0.230(P2O5)0.770, in order to determine Gd…Gd separations in its local structure. The minimum rare-earth separation is of particular interest given that the optical properties of these glasses can quench when rare-earth ions become too close to each other. To this end, a weak Gd…Gd pairwise correlation is located at 4.2(1) Å which is representative of a meta-phosphate R…R separation. More intense first neighbor Gd…Gd pairwise correlations are found at the larger radial distributions, 4.8(1) Å, 5.1(1) Å and 5.4(1) Å. These reflect a mixedmore » ultra-phosphate and meta-phosphate structural character, respectively. A second neighbor Gd…Gd pairwise correlation lies at 6.6(1) Å which is indicative of meta-phosphate structures. Meta- and ultra-phosphate classifications are made by comparing the R…R separations against those of rare-earth phosphate crystal structures, R(PO3)3 and RP5O14 respectively, or difference pair distribution function (ΔPDF) features determined on similar glasses using difference neutron scattering methods. The local structure of this glass is therefore found to display multiple rare-earth ion environments, presumably because its composition lies between these two stoichiometric formulae. These Gd…Gd separations are well resolved in the ΔPDFs that represent the AXS signal. Indeed, the spatial resolution is so good that it also enables the identification of R…X (X = R, P, O) pairwise correlations up to r ~ 9 Å; their average separations lie at r ~ 7.1(1) Å, 7.6(1) Å 7.9(1) Å, 8.4(1) Å and 8.7(1) Å. This is the first report of a Gd K-edge AXS study on an amorphous material. Its demonstrated ability to characterize the local structure of a glass up to such a long-range of r, heralds exciting prospects for AXS studies on other ternary non-crystalline materials. However, the technical challenge of such an

  11. Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean NOx Trap Catalysts: A Combined H2 Temperature-Programmed Reaction, in Situ Sulfur K-Edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

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

    Kim, D.H.; Hanson, J.; Szanyi, J.

    2009-04-30

    Desulfation by hydrogen of presulfated Pt (2 wt %)-BaO(20 wt %)/Al{sub 2}O{sub 3} with various sulfur loading (S/Ba = 0.12, 0.31, and 0.62) were investigated by combining H{sub 2} temperature programmed reaction (TPRX), X-ray photoelectron spectroscopy (XPS), in situ sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved X-ray diffraction (TR-XRD) techniques. We find that the amount of H{sub 2}S desorbed during the desulfation in the H{sub 2} TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates weremore » transformed to a BaS phase and remained in the catalyst rather than being removed as H{sub 2}S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H{sub 2}S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H{sub 2}O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H{sub 2}S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt-BaO/Al{sub 2}O{sub 3} lean NO{sub x} trap catalysts is markedly dependent on the sulfation levels.« less

  12. Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

    2016-05-01

    Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

  13. A feasibility study of heat-pipe-cooled leading edges for hypersonic cruise aircraft

    NASA Technical Reports Server (NTRS)

    Silverstein, C. C.

    1971-01-01

    A theoretical study of the use of heat pipe structures for cooling the leading edges of hypersonic cruise aircraft was carried out over a Mach number range of 6 to 12. Preliminary design studies showed that a heat pipe cooling structure with a 33-in. chordwise length could maintain the maximum temperature of a 65 deg sweepback wing with a 0.5-in. leading edge radius below 1600 F during cruise at Mach 8. A few relatively minor changes in the steady-state design of the structure were found necessary to insure satisfactory cooling during the climb to cruise speed and altitude. It was concluded that heat pipe cooling is an attractive, feasible technique for limiting leading edge temperatures of hypersonic cruise aircraft.

  14. Cleaved-edge-overgrowth nanogap electrodes.

    PubMed

    Luber, Sebastian M; Bichler, Max; Abstreiter, Gerhard; Tornow, Marc

    2011-02-11

    We present a method to fabricate multiple metal nanogap electrodes of tailored width and distance in parallel, on the cleaved plane of a GaAs/AlGaAs heterostructure. The three-dimensional patterned structures are obtained by a combination of molecular-beam-epitaxial regrowth on a crystal facet, using the cleaved-edge-overgrowth (CEO) method, and subsequent wet selective etching and metallization steps. SEM and AFM studies reveal smooth and co-planar electrodes of width and distance of the order of 10 nm. Preliminary electrical characterization indicates electrical gap insulation in the 100 MΩ range with kΩ lead resistance. We propose our methodology to realize multiple electrode geometries that would allow investigation of the electrical conductivity of complex nanoscale objects such as branched organic molecules.

  15. Forests on the edge: Microenvironmental drivers of carbon cycle response to edge effects

    NASA Astrophysics Data System (ADS)

    Reinmann, A.; Hutyra, L.; Smith, I. A.; Thompson, J.

    2017-12-01

    Twenty percent of the world's forest is within 100 m of a forest edge, but much of our understanding of forest carbon (C) cycling comes from large, intact ecosystems, which creates an important mismatch between the landscapes we study and those we aim to characterize. The temperate broadleaf forest is the most heavily fragmented forest biome in the world and its growth and carbon storage responses to forest edge effects appear to be the opposite of those in the tropical and boreal regions. We used field measurements to quantify the drivers of temperate forest C cycling response to edge effects, characterizing vegetative growth, respiration, and forest structure. We find large gradients in air and soil temperature from the forest interior to edge (up to 4 and 10° C, respectively) and the magnitude of this gradient is inversely correlated to the size of the forest edge growth enhancement. Further, leaf area index increases with proximity to the forest edge. While we also find increases in soil respiration between the forest interior and edge, this flux is small relative to aboveground growth enhancement near the edge. These findings represent an important advancement in our understanding of forest C cycle response to edge effects and will greatly improve our capacity to constrain biogenic C fluxes in fragmented and heterogeneous landscapes.

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

    PubMed

    Fransson, Thomas; Burdakova, Daria; Norman, Patrick

    2016-05-21

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

  17. 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

  18. Numerical analysis of the impact of permeability on trailing-edge noise

    NASA Astrophysics Data System (ADS)

    Koh, Seong Ryong; Meinke, Matthias; Schröder, Wolfgang

    2018-05-01

    The impact of porous surfaces on the near-wall turbulent structures and the generated trailing-edge noise is analyzed for several trailing-edge shapes of finite thickness using a high resolution large-eddy simulation (LES)/computational aeroacoustics (CAA) method. The porous surface of the trailing edge is defined by the porosity and the viscous permeability determined by the solution of a turbulent flat plate boundary layer at a Reynolds number 1280 based on the displacement thickness in the inflow cross section. The volume-averaged approach for the homogeneous porous medium shows that the porous impedance scales linearly with the porosity and exponentially with the mean structure size of a porous medium. The drag induced by the porous surface changes the friction velocity and the permeability Reynolds number ReK which determines the porous impedance Rs scaled by ReK-2/3. The trailing-edge noise is analyzed for three solid and three porous trailing edges. The effect of a finite span is investigated by the spanwise correlation model based on the measured coherence distribution. The acoustic prediction shows a good agreement with measurements of the broadband spectrum and the strong tone generated by a finite trailing-edge thickness. The pressure gradient inside the porous media is redistributed by the Darcy drag defined by the viscous permeability and the porosity. The mean pressure increases in the upstream direction inside the porous medium such that the flow acceleration involved in the acoustic generation is reduced inside the porous medium. The noise reduction by a porous medium reaches 11 dB for the trailing-edge shape which possesses a sharp corner for the solid surface. The porous surface applied to a semi-circular trailing edge achieves a 4 dB noise reduction. The directivity pattern for individual components of the acoustic spectrum shows that the massive noise reduction is determined at the tone. Enhanced wave diffraction by the thick flat plate changes

  19. Pristine Basal- and Edge-Plane-Oriented Molybdenite MoS2 Exhibiting Highly Anisotropic Properties.

    PubMed

    Tan, Shu Min; Ambrosi, Adriano; Sofer, Zdenĕk; Huber, Štěpán; Sedmidubský, David; Pumera, Martin

    2015-05-04

    The layered structure of molybdenum disulfide (MoS2 ) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2 : basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k(0) of 4.96×10(-5) and 1.1×10(-3)  cm s(-1) for [Fe(CN)6 ](3-/4-) and [Ru(NH3 )6 ](3+/2+) redox probes, respectively, compared to the basal plane, which yielded k(0) tending towards zero for [Fe(CN)6 ](3-/4-) and about 9.3×10(-4)  cm s(-1) for [Ru(NH3 )6 ](3+/2+) . The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6 ](3-/4-) in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Edge detection and localization with edge pattern analysis and inflection characterization

    NASA Astrophysics Data System (ADS)

    Jiang, Bo

    2012-05-01

    In general edges are considered to be abrupt changes or discontinuities in two dimensional image signal intensity distributions. The accuracy of front-end edge detection methods in image processing impacts the eventual success of higher level pattern analysis downstream. To generalize edge detectors designed from a simple ideal step function model to real distortions in natural images, research on one dimensional edge pattern analysis to improve the accuracy of edge detection and localization proposes an edge detection algorithm, which is composed by three basic edge patterns, such as ramp, impulse, and step. After mathematical analysis, general rules for edge representation based upon the classification of edge types into three categories-ramp, impulse, and step (RIS) are developed to reduce detection and localization errors, especially reducing "double edge" effect that is one important drawback to the derivative method. But, when applying one dimensional edge pattern in two dimensional image processing, a new issue is naturally raised that the edge detector should correct marking inflections or junctions of edges. Research on human visual perception of objects and information theory pointed out that a pattern lexicon of "inflection micro-patterns" has larger information than a straight line. Also, research on scene perception gave an idea that contours have larger information are more important factor to determine the success of scene categorization. Therefore, inflections or junctions are extremely useful features, whose accurate description and reconstruction are significant in solving correspondence problems in computer vision. Therefore, aside from adoption of edge pattern analysis, inflection or junction characterization is also utilized to extend traditional derivative edge detection algorithm. Experiments were conducted to test my propositions about edge detection and localization accuracy improvements. The results support the idea that these edge

  1. Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis

    NASA Astrophysics Data System (ADS)

    Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

    2012-02-01

    Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

  2. Big-data-based edge biomarkers: study on dynamical drug sensitivity and resistance in individuals.

    PubMed

    Zeng, Tao; Zhang, Wanwei; Yu, Xiangtian; Liu, Xiaoping; Li, Meiyi; Chen, Luonan

    2016-07-01

    Big-data-based edge biomarker is a new concept to characterize disease features based on biomedical big data in a dynamical and network manner, which also provides alternative strategies to indicate disease status in single samples. This article gives a comprehensive review on big-data-based edge biomarkers for complex diseases in an individual patient, which are defined as biomarkers based on network information and high-dimensional data. Specifically, we firstly introduce the sources and structures of biomedical big data accessible in public for edge biomarker and disease study. We show that biomedical big data are typically 'small-sample size in high-dimension space', i.e. small samples but with high dimensions on features (e.g. omics data) for each individual, in contrast to traditional big data in many other fields characterized as 'large-sample size in low-dimension space', i.e. big samples but with low dimensions on features. Then, we demonstrate the concept, model and algorithm for edge biomarkers and further big-data-based edge biomarkers. Dissimilar to conventional biomarkers, edge biomarkers, e.g. module biomarkers in module network rewiring-analysis, are able to predict the disease state by learning differential associations between molecules rather than differential expressions of molecules during disease progression or treatment in individual patients. In particular, in contrast to using the information of the common molecules or edges (i.e.molecule-pairs) across a population in traditional biomarkers including network and edge biomarkers, big-data-based edge biomarkers are specific for each individual and thus can accurately evaluate the disease state by considering the individual heterogeneity. Therefore, the measurement of big data in a high-dimensional space is required not only in the learning process but also in the diagnosing or predicting process of the tested individual. Finally, we provide a case study on analyzing the temporal expression

  3. Effect of different thickness crystalline SiC buffer layers on the ordering of MgB{sub 2} films probed by extended x-ray absorption fine structure

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

    Putri, W. B. K.; Tran, D. H.; Kang, B., E-mail: bwkang@chungbuk.ac.kr

    2014-03-07

    Extended X-ray absorption fine structure (EXAFS) spectroscopy is a powerful method to investigate the local structure of thin films. Here, we have studied EXAFS of MgB{sub 2} films grown on SiC buffer layers. Crystalline SiC buffer layers with different thickness of 70, 100, and 130 nm were deposited on the Al{sub 2}O{sub 3} (0001) substrates by using a pulsed laser deposition method, and then MgB{sub 2} films were grown on the SiC buffer layer by using a hybrid physical-chemical vapor deposition technique. Transition temperature of MgB{sub 2} film decreased with increasing thickness of SiC buffer layer. However, the T{sub c} droppingmore » went no farther than 100 nm-thick-SiC. This uncommon behavior of transition temperature is likely to be created from electron-phonon interaction in MgB{sub 2} films, which is believed to be related to the ordering of MgB{sub 2} atomic bonds, especially in the ordering of Mg–Mg bonds. Analysis from Mg K-edge EXAFS measurements showed interesting ordering behavior of MgB{sub 2} films. It is noticeable that the ordering of Mg–B bonds is found to decrease monotonically with the increase in SiC thickness of the MgB{sub 2} films, while the opposite happens with the ordering in Mg–Mg bonds. Based on these results, crystalline SiC buffer layers in MgB{sub 2} films seemingly have evident effects on the alteration of the local structure of the MgB{sub 2} film.« less

  4. Stress and efficiency studies in edge-defined film-fed growth

    NASA Technical Reports Server (NTRS)

    Kalejs, J.

    1986-01-01

    The progress was reviewed for stress and efficiency studies of edge-defined film-fed growth (EFG) material. Effort was concentrated on the definition of condiitions that will reduce stress, on quantifying dislocation electrical activity and limits on solar cell efficiency, and on studying the effects of dopants on EFG characteristics.

  5. Lead is not off center in PbTe: the importance of r-space phase information in extended x-ray absorption fine structure spectroscopy.

    PubMed

    Keiber, T; Bridges, F; Sales, B C

    2013-08-30

    PbTe is a well-known thermoelectric material. Recent x-ray total scattering studies suggest that Pb moves off center along 100 in PbTe, by ∼0.2  Å at 300 K, producing a split Pb-Te pair distribution. We present an extended x-ray absorption fine structure spectroscopy (EXAFS) study of PbTe (and Tl doped PbTe) to determine if Pb or Te is off center. EXAFS provides sensitive r- or k-space phase information which can differentiate between a split peak for the Pb-Te distribution (indicative of off-center Pb) and a thermally broadened peak. We find no evidence for a split peak for Pb-Te or Te-Pb. At 300 K, the vibration amplitude for Pb-Te (or Te-Pb) is large; this thermally induced disorder is indicative of weak bonds, and the large disorder is consistent with the low thermal conductivity at 300 K. We also find evidence of an anharmonic potential for the nearest Pb-Te bonds, consistent with the overall anharmonicity found for the phonon modes. This effect is modeled by a "skew" factor (C3) which significantly improves the fit of the Pb-Te and Te-Pb peaks for the high temperature EXAFS data; C3 becomes significant above approximately 150-200 K. The consequences of these results will be discussed.

  6. Mortality after percutaneous edge-to-edge mitral valve repair: a contemporary review.

    PubMed

    Kortlandt, Friso A; de Beenhouwer, Thomas; Swaans, Martin J; Post, Marco C; van der Heyden, Jan A S; Eefting, Frank D; Rensing, Benno J W M

    2016-04-01

    Percutaneous edge-to-edge mitral valve (MV) repair is a relatively new treatment option for mitral regurgitation (MR). After the feasibility and safety having been proved in low-surgical-risk patients, the use of this procedure has shifted more to the treatment of high-risk patients. With the absence of randomized controlled trials (RCT) for this particular subgroup, observational studies try to add evidence to the safety aspect of this procedure. These also provide short- and mid-term mortality figures. Several mortality predictors have been identified, which may help the optimal selection of patients who will benefit most from this technique. In this article we provide an overview of the literature about mortality and its predictors in patients treated with the percutaneous edge-to-edge device.

  7. 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.

  8. Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

    NASA Astrophysics Data System (ADS)

    Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

    2016-06-01

    Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

  9. Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

    1996-04-01

    The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

  10. 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.

  11. NbN/MgO/NbN edge-geometry tunnel junctions

    NASA Technical Reports Server (NTRS)

    Hunt, B. D.; Leduc, H. G.; Cypher, S. R.; Stern, J. A.; Judas, A.

    1989-01-01

    The fabrication and low-frequency testing of the first edge-geometry NbN/MgO/NbN superconducting tunnel junctions are reported. The use of an edge geometry allows very small junction areas to be obtained, while the all-NbN electrodes permit operation at 8-10 K with a potential maximum operating frequency above 1 THz. Edge definition in the base NbN film was accomplished utilizing Ar ion milling with an Al2O3 milling mask, followed by a lower energy ion cleaning step. This process has produced all-refractory-material tunnel junctions with areas as small as 0.1 sq micron, resistance-area products less than 21 ohm sq micron, and subgap to normal state resistance ratios larger than 18.

  12. An experimental study of airfoil instability tonal noise with trailing edge serrations

    NASA Astrophysics Data System (ADS)

    Chong, Tze Pei; Joseph, Phillip F.

    2013-11-01

    This paper presents an experimental study of the effect of trailing edge serrations on airfoil instability noise. Detailed aeroacoustic measurements are presented of the noise radiated by an NACA-0012 airfoil with trailing edge serrations in a low to moderate speed flow under acoustical free field conditions. The existence of a separated boundary layer near the trailing edge of the airfoil at an angle of attack of 4.2 degree has been experimentally identified by a surface mounted hot-film arrays technique. Hot-wire results have shown that the saw-tooth surface can trigger a bypass transition and prevent the boundary layer from becoming separated. Without the separated boundary layer to act as an amplifier for the incoming Tollmien-Schlichting waves, the intensity and spectral characteristic of the radiated tonal noise can be affected depending upon the serration geometry. Particle Imaging Velocimetry (PIV) measurements of the airfoil wakes for a straight and serrated trailing edge are also reported in this paper. These measurements show that localized normal-component velocity fluctuations that are present in a small region of the wake from the laminar airfoil become weakened once serrations are introduced. Owing to the above unique characteristics of the serrated trailing edges, we are able to further investigate the mechanisms of airfoil instability tonal noise with special emphasis on the assessment of the wake and non-wake based aeroacoustic feedback models. It has been shown that the instability tonal noise generated at an angle of attack below approximately one degree could involve several complex mechanisms. On the other hand, the non-wake based aeroacoustic feedback mechanism alone is sufficient to predict all discrete tone frequencies accurately when the airfoil is at a moderate angle of attack. Larger Δf, which is defined as (fn+1-fn). In other words, a larger margin of velocity increase is required in order to "shift" the fn and fn+1 across fs

  13. Supersonic Leading Edge Receptivity

    NASA Technical Reports Server (NTRS)

    Maslov, Anatoly A.

    1998-01-01

    This paper describes experimental studies of leading edge boundary layer receptivity for imposed stream disturbances. Studies were conducted in the supersonic T-325 facility at ITAM and include data for both sharp and blunt leading edges. The data are in agreement with existing theory and should provide guidance for the development of more complete theories and numerical computations of this phenomena.

  14. Characterisation of edge turbulence in relation to edge magnetic field configuration in L-mode plasmas in the Mega Amp Spherical Tokamak.

    NASA Astrophysics Data System (ADS)

    Dewhurst, J.; Hnat, B.; Dudson, B.; Dendy, R. O.; Counsell, G. F.; Kirk, A.

    2007-12-01

    Almost all astrophysical and magnetically confined fusion plasmas are turbulent. Here, we examine ion saturation current (Isat) measurements of edge plasma turbulence for three MAST L-mode plasmas that differ primarily in their edge magnetic field configurations. First, absolute moments of the coarse grained data are examined to obtain accurate values of scaling exponents. The dual scaling behaviour is identified in all samples, with the temporal scale τ ≍ 40-60 μs separating the two regimes. Strong universality is then identified in the functional form of the probability density function (PDF) for Isat fluctuations, which is well approximated by the Fréchet distribution on temporal scales τ ≤ 40μs. For temporal scales τ > 40μs, the PDFs appear to converge to the Gumbel distribution, which has been previously identified as a universal feature of many other complex phenomena. The optimal fitting parameters k=1.15 for Fréchet and a=1.35 for Gumbel provide a simple quantitative characterisation of the full spectrum of fluctuations. We conclude that, to good approximation, the properties of the edge turbulence are independent of the edge magnetic field configuration.

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  16. Transaortic Alfieri Edge-to-Edge Repair for Functional Mitral Regurgitation.

    PubMed

    Imasaka, Ken-Ichi; Tayama, Eiki; Morita, Shigeki; Toriya, Ryohei; Tomita, Yukihiro

    2018-03-01

    There is controversy about handling functional mitral regurgitation in patients undergoing aortic valve or proximal aortic operations. We describe a transaortic Alfieri edge-to-edge repair for functional mitral regurgitation that reduces operative excessive invasion and prolonged cardiopulmonary bypass time. Between May 2013 and December 2016, 10 patients underwent transaortic Alfieri edge-to-edge mitral repair. There were no operative deaths. The severity of mitral regurgitation immediately after the operation by transesophageal echocardiography was none or trivial in all patients. A transaortic Alfieri edge-to-edge repair for functional mitral regurgitation is a simple and safe approach. Copyright © 2018 The Society of Thoracic Surgeons. Published by Elsevier Inc. All rights reserved.

  17. Edge-effect interactions in fragmented and patchy landscapes.

    PubMed

    Porensky, Lauren M; Young, Truman P

    2013-06-01

    Ecological edges are increasingly recognized as drivers of landscape patterns and ecosystem processes. In fragmented and patchy landscapes (e.g., a fragmented forest or a savanna with scattered termite mounds), edges can become so numerous that their effects pervade the entire landscape. Results of recent studies in such landscapes show that edge effects can be altered by the presence or proximity of other nearby edges. We considered the theoretical significance of edge-effect interactions, illustrated various landscape configurations that support them and reviewed existing research on this topic. Results of studies from a variety of locations and ecosystem types show that edge-effect interactions can have significant consequences for ecosystems and conservation, including higher tree mortality rates in tropical rainforest fragments, reduced bird densities in grassland fragments, and bush encroachment and reduced wildlife densities in a tropical savanna. To clarify this underappreciated concept and synthesize existing work, we devised a conceptual framework for edge-effect interactions. We first worked to reduce terminological confusion by clarifying differences among terms such as edge intersection and edge interaction. For cases in which nearby edge effects interact, we proposed three possible forms of interaction: strengthening (presence of a second edge causes stronger edge effects), weakening (presence of a second edge causes weaker edge effects), and emergent (edge effects change completely in the presence of a second edge). By clarifying terms and concepts, this framework enables more precise descriptions of edge-effect interactions and facilitates comparisons of results among disparate study systems and response variables. A better understanding of edge-effect interactions will pave the way for more appropriate modeling, conservation, and management in complex landscapes. © 2013 Society for Conservation Biology.

  18. Infective endocarditis following transcatheter edge-to-edge mitral valve repair: A systematic review.

    PubMed

    Asmarats, Lluis; Rodriguez-Gabella, Tania; Chamandi, Chekrallah; Bernier, Mathieu; Beaudoin, Jonathan; O'Connor, Kim; Dumont, Eric; Dagenais, François; Paradis, Jean-Michel; Rodés-Cabau, Josep

    2018-05-10

    To assess the clinical characteristics, management, and outcomes of patients diagnosed with infective endocarditis (IE) after edge-to-edge mitral valve repair with the MitraClip device. Transcatheter edge-to-edge mitral valve repair has emerged as an alternative to surgery in high-risk patients. However, few data exist on IE following transcatheter mitral procedures. Four electronic databases (PubMed, Google Scholar, Embase, and Cochrane Library) were searched for original published studies on IE after edge-to-edge transcatheter mitral valve repair from 2003 to 2017. A total of 10 publications describing 12 patients with definitive IE (median age 76 years, 55% men) were found. The mean logistic EuroSCORE/EuroSCORE II were 41% and 45%, respectively. The IE episode occurred early (within 12 months post-procedure) in nine patients (75%; within the first month in five patients). Staphylococcus aureus was the most frequent (60%) causal microorganism, and severe mitral regurgitation was present in all cases but one. Surgical mitral valve replacement (SMVR) was performed in most (67%) patients, and the mortality associated with the IE episode was high (42%). IE following transcatheter edge-to-edge mitral valve repair is a rare but life-threatening complication, usually necessitating SMVR despite the high-risk profile of the patients. These results highlight the importance of adequate preventive measures and a prompt diagnosis and treatment of this serious complication. © 2018 Wiley Periodicals, Inc.

  19. Electron magnetic resonance and magnetooptical studies of nanoparticle-containing borate glasses

    NASA Astrophysics Data System (ADS)

    Kliava, Janis; Edelman, Irina; Ivanova, Oxana; Ivantsov, Ruslan; Petrakovskaja, Eleonora; Hennet, Louis; Thiaudière, Dominique; Saboungi, Marie-Louise

    2011-03-01

    We report electron magnetic resonance (EMR) and magnetooptical studies of borate glasses of molar composition 22.5K 2O-22.5Al 2O 3-55B 2O 3 co-doped with low concentrations of Fe 2O 3 and MnO. In as-prepared samples the paramagnetic ions, as a rule, are in diluted state. However, in the case where the ratio of the iron and manganese oxides in the charge is 3/2, magnetic nanoparticles with characteristics close to those of manganese ferrite are formed already at the first stage of the glass preparation, as evidenced by both magnetic circular dichroism (MCD) and EMR. After thermal treatment all glasses show characteristic MCD and EMR spectra, attesting to the presence of magnetic nanoparticles, predominantly including iron ions. Preliminary EXAFS measurements at the Fe K-absorption edge show an emergence of nanoparticles with a structure close to MnFe 2O 4 after annealing the glasses at 560 °C. By computer simulating the EMR spectra at variable temperatures, a superparamagnetic nature of relatively broad size and shape distribution with the average diameter of ca. 3-4 nm. The characteristic temperature-dependent shift of the apparent resonance field is explained by a strong temperature dependence of the magnetic anisotropy in the nanoparticles. The formation of magnetic nanoparticles confers to the potassium-alumina-borate glasses magnetic and magneto-optical properties typical of magnetically ordered substances. At the same time, they remain transparent in a part of the visible and near infrared spectral range and display a high Faraday rotation value.

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

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

    Younker, J.M.; Krest, C.M.; Jiang, W.

    2009-05-28

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