Subgap Absorption in Conjugated Polymers

DOE R&D Accomplishments Database

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

1991-01-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

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

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

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

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

1996-01-10

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

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

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

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

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

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

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

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

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

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.

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

DOE PAGES

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

2017-07-27

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

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

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.

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

PubMed Central

2015-01-01

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference between formal oxidation state and metal Zeff or, as in the case of [WIV(mdt)2(CO)2], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere. PMID:25068843

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

PubMed

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

2014-08-18

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

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

Detection of metal stress in boreal forest species using the 0.67-micron chlorophyll absorption band

NASA Technical Reports Server (NTRS)

Singhroy, Vernon H.; Kruse, Fred A.

1991-01-01

Several recent studies have shown that a shift of the red-edge inflection near 0.70 micron in vegetation reflectance spectra is an indicator of metal stress, partially attributable to changes in chlorophyll concentration. This 'red-edge shift', however, is difficult to detect and has been reported both toward longer (red) and shorter (blue) wavelengths. Our work demonstrates that direct measurement of the depth and width of the chlorophyll absorption band at 0.67 micron using digital feature extraction and absorption band characterization procedures developed for the analysis of mineral spectra is a more consistent indicator of metal stress. Additionally, the magnitude of these parameters is generally greater than that of the red edge shift and thus should be more amenable to detection and mapping using field and aircraft spectrometers.

The interaction of copper ions with Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli: an X-ray absorption near-edge structure (XANES) spectroscopy study.

PubMed

Zanzen, Ulrike; Bovenkamp-Langlois, Lisa; Klysubun, Wantana; Hormes, Josef; Prange, Alexander

2018-04-01

The antimicrobial properties of copper ions have been known for a long time. However, the exact mechanism of action of the transition metal on microorganisms has long been unclear. X-ray absorption near-edge structure (XANES) spectroscopy at the Cu K edge allows the determination of copper speciation in Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa that have been treated with Cu(II) and Cu(I) solutions. The death/inactivation of the bacteria was observed using plate counting and light microscopy. The Cu K-XANES spectra of the two Gram-negative bacteria are different than those of the Gram-positive strain. The results clearly show that the Cu + -S bond contributes to the antibacterial activity of copper, as in the case of silver. The detailed evaluation of the differentiated absorption spectra shows that Cu + (not Cu 2+ ) is the dominant ion that binds to the bacteria. Because Cu + is not the most common copper ion, copper is not as effective an antibacterial agent as silver, whose common valency is actually + 1. Any reaction of copper with phosphorus from the bacteria can be excluded after the evaluation of the absorption spectra.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra.

PubMed

Vilas, F; Gaffey, M J

1989-11-10

Absorption features having depths up to 5% are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra

NASA Technical Reports Server (NTRS)

Vilas, Faith; Gaffey, Michael J.

1989-01-01

Absorption features having depths up to 5 percent are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

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.

Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

PubMed

Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

2018-04-10

X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

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.

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.

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

NASA Astrophysics Data System (ADS)

Terada, Hiroshi; Tokunaga, Alan T.

2017-01-01

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

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

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

Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye

2015-09-17

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

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

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

PubMed

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

2018-04-19

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

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.

Spectroscopic ellipsometry characterization of ZnO:Sn thin films with various Sn composition deposited by remote-plasma reactive sputtering

NASA Astrophysics Data System (ADS)

Janicek, Petr; Niang, Kham M.; Mistrik, Jan; Palka, Karel; Flewitt, Andrew J.

2017-11-01

ZnO:Sn thin films were deposited onto thermally oxidized silicon substrates using a remote plasma reactive sputtering. Their optical constants (refractive index n and extinction coefficient k) were determined from ellipsometric data recorded over a wide spectral range (0.05-6 eV). Parametrization of ZnO:Sn complex dielectric permittivity consists of a parameterized semiconductor oscillator function describing the short wavelength absorption edge, a Drude oscillator describing free carrier absorption in near-infrared part of spectra and a Lorentz oscillator describing the long wavelength absorption edge and intra-band absorption in the ultra-violet part of the spectra. Using a Mott-Davis model, the increase in local disorder with increasing Sn doping is quantified from the short wavelength absorption edge onset. Using the Wemple-DiDomenico single oscillator model for the transparent part of the optical constants spectra, an increase in the centroid distance of the valence and conduction bands with increasing Sn doping is shown and only slight increase in intensity of the inter-band optical transition due to Sn doping occurs. The Drude model applied in the near-infrared part of the spectra revealed the free carrier concentration and mobility of ZnO:Sn. Results show that the range of transparency of prepared ZnO:Sn layers is not dramatically affected by Sn doping whereas electrical conductivity could be controlled by Sn doping. Refractive index in the transparent part is comparable with amorphous Indium Gallium Zinc Oxide allowing utilization of prepared ZnO:Sn layers as an indium-free alternative.

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

PubMed

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

2011-05-12

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

The 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.

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

PubMed

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

2001-03-01

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

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

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

PubMed Central

Kubin, Markus; Kern, Jan; Gul, Sheraz; Kroll, Thomas; Chatterjee, Ruchira; Löchel, Heike; Fuller, Franklin D.; Sierra, Raymond G.; Quevedo, Wilson; Weniger, Christian; Rehanek, Jens; Firsov, Anatoly; Laksmono, Hartawan; Weninger, Clemens; Alonso-Mori, Roberto; Nordlund, Dennis L.; Lassalle-Kaiser, Benedikt; Glownia, James M.; Krzywinski, Jacek; Moeller, Stefan; Turner, Joshua J.; Minitti, Michael P.; Dakovski, Georgi L.; Koroidov, Sergey; Kawde, Anurag; Kanady, Jacob S.; Tsui, Emily Y.; Suseno, Sandy; Han, Zhiji; Hill, Ethan; Taguchi, Taketo; Borovik, Andrew S.; Agapie, Theodor; Messinger, Johannes; Erko, Alexei; Föhlisch, Alexander; Bergmann, Uwe; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe

2017-01-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. PMID:28944255

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

DOE PAGES

Kubin, Markus; Kern, Jan; Gul, Sheraz; ...

2017-09-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. But, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexesmore » (Mn ~ 6-15 mmol/l) with no visible effects of radiation damage. We then present the first L-edge absorption spectra of the oxygen evolving complex (Mn 4 CaO 5 ) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.« less

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

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

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

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

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

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

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

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

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

NASA Astrophysics Data System (ADS)

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

2014-04-01

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

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

PubMed Central

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

2014-01-01

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

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

DOE PAGES

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

2014-04-17

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

Modification of fluorescence and optical properties of Rhodamine B dye doped PVA/Chitosan polymer blend films

NASA Astrophysics Data System (ADS)

Padmakumari, R.; Ravindrachary, V.; Mahantesha, B. K.; Sagar, Rohan N.; Sahanakumari, R.; Bhajantri, R. F.

2018-05-01

Pure and Rhodamine B doped Poly (vinyl alcohol)/Chitosan composite films are prepared using solution casting method. Fourier transforms infrared spectra (FTIR), Ultraviolet-Visible (UV-Vis), fluorescence studies were used to characterize the prepared polymer films. The FT-IR results show that the appearance of new peaks along with shift in peak positions indicates the interaction of Rhodamine B with PVA-CS blend. Optical absorption edge, band gap and activation energy were determined from UV-Visible studies. The optical absorption edge increases, band gap decreases and activation energy increases with dopant concentration respectively. The corresponding emission spectra were studied using fluorescence spectroscopy. From the fluorescence study the quenching phenomena are observed in emission wavelength range of 607nm-613nm upon excitation with absorption maxima 443nm.

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

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

Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina

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

Determining thin film properties by fitting optical transmittance

NASA Astrophysics Data System (ADS)

Klein, J. D.; Yen, A.; Cogan, S. F.

1990-08-01

The optical transmission spectra of rf sputtered tungsten oxide films on glass substrates were modeled to determine absorption edge behavior, film thickness, and index of refraction. Removal of substrate reflection and absorption phenomena from the experimental spectra allowed direct examination of thin film optical characteristics. The interference fringe pattern allows determination of the film thickness and the dependence of the real index of refraction on wavelength. Knowledge of the interference fringe behavior in the vicinity of the absorption edge was found essential to unambiguous determination of the optical band gap. In particular, the apparently random deviations commonly observed in the extrapolation of as-acquired data are eliminated by explicitly considering interference fringe phenomena. The multivariable optimization fitting scheme employed allows air-film-substrate reflection losses to be compensated without making reflectance measurements.

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

DOE PAGES

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

2018-03-23

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

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).

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

NASA Astrophysics Data System (ADS)

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

1990-11-01

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

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.

Near sulfur L-edge X-ray absorption spectra of methanethiol in isolation and adsorbed on a Au(111) surface: a theoretical study using the four-component static exchange approximation.

PubMed

Villaume, Sebastien; Ekström, Ulf; Ottosson, Henrik; Norman, Patrick

2010-06-07

The relativistic four-component static exchange approach for calculation of near-edge X-ray absorption spectra has been reviewed. Application of the method is made to the Au(111) interface and the adsorption of methanethiol by a study of the near sulfur L-edge spectrum. The binding energies of the sulfur 2p(1/2) and 2p(3/2) sublevels in methanethiol are determined to be split by 1.2 eV due to spin-orbit coupling, and the binding energy of the 2p(3/2) shell is lowered from 169.2 eV for the isolated system to 167.4 and 166.7-166.8 eV for methanethiol in mono- and di-coordinated adsorption sites, respectively (with reference to vacuum). In the near L-edge X-ray absorption fine structure spectrum only the sigma*(S-C) peak at 166 eV remains intact by surface adsorption, whereas transitions of predominantly Rydberg character are largely quenched in the surface spectra. The sigma*(S-H) peak of methanethiol is replaced by low-lying, isolated, sigma*(S-Au) peak(s), where the number of peaks in the latter category and their splittings are characteristic of the local bonding situation of the sulfur.

Temperature behaviour of optical parameters in (Ag3AsS3)0.3(As2S3)0.7 thin films

NASA Astrophysics Data System (ADS)

Kutsyk, Mykhailo M.; Ráti, Yosyp Y.; Izai, Vitalii Y.; Makauz, Ivan I.; Studenyak, Ihor P.; Kökényesi, Sandor; Komada, Paweł; Zhailaubayev, Yerkin; Smailov, Nurzhigit

2015-12-01

(Ag3AsS3)0.3(As2S3)0.7 thin films were deposited onto a quartz substrate by rapid thermal evaporation. The optical transmission spectra of thin films were measured in the temperature range 77-300 K. It is shown that the absorption edge spectra are described by the Urbach rule. The temperature behaviour of absorption spectra was studied, the temperature dependences of energy position of absorption edge and Urbach energy were investigated. The influence of transition from three-dimensional glass to the two-dimensional thin film as well as influence of Ag3AsS3 introduction into As2S3 on the optical parameters of (Ag3AsS3)0.3(As2S3)0.7 were analysed. The spectral and temperature behaviour or refractive index for (Ag3AsS3)0.3(As2S3)0.7 thin film were studied.

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

USGS Publications Warehouse

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

2011-01-01

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

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

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

Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke

2016-03-07

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

Simulating Ru L3-edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

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

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-01

Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+,more » [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.« less

The Electronic Structure of Mn in Oxides, Coordination Complexes, and the Oxygen-Evolving Complex of Photosystem II Studied by Resonant Inelastic X-ray Scattering

PubMed Central

Yano, Junko; Visser, Hendrik; Robblee, John H.; Gu, Weiwei; de Groot, Frank M. F.; Christou, George; Pecoraro, Vincent L.

2014-01-01

Resonant inelastic X-ray scattering (RIXS) was used to collect Mn K pre-edge spectra and to study the electronic structure in oxides, molecular coordination complexes, as well as the S1 and S2 states of the oxygen-evolving complex (OEC) of photosystem II (PS II). The RIXS data yield two-dimensional plots that can be interpreted along the incident (absorption) energy or the energy transfer axis. The second energy dimension separates the pre-edge (predominantly 1s to 3d transitions) from the main K-edge, and a detailed analysis is thus possible. The 1s2p RIXS final-state electron configuration along the energy transfer axis is identical to conventional L-edge absorption spectroscopy, and the RIXS spectra are therefore sensitive to the Mn spin state. This new technique thus yields information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, i.e., (3d,3d) and (2p,3d) two-electron interactions are crucial to describe the spectral shapes in all systems. We propose to explain the shift of the K pre-edge absorption energy upon Mn oxidation in terms of the effective number of 3d electrons (fractional 3d orbital population). The spectral changes in the Mn 1s2p3/2 RIXS spectra between the PS II S1 and S2 states are small compared to that of the oxides and two of the coordination complexes (MnIII(acac)3 and MnIV(sal)2(bipy)). We conclude that the electron in the step from S1 to S2 is transferred from a strongly delocalized orbital. PMID:15303869

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

DOE PAGES

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

2018-04-24

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

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

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

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

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

Anomalous small-angle scattering as a way to solve the Babinet principle problem

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

Boiko, M. E., E-mail: m.e.boiko@mail.ioffe.ru; Sharkov, M. D.; Boiko, A. M.

2013-12-15

X-ray absorption spectra (XAS) have been used to determine the absorption edges of atoms present in a sample under study. A series of small-angle X-ray scattering (SAXS) measurements using different monochromatic X-ray beams at different wavelengths near the absorption edges is performed to solve the Babinet principle problem. The sizes of clusters containing atoms determined by the method of XAS were defined in SAXS experiments. In contrast to differential X-ray porosimetry, anomalous SAXS makes it possible to determine sizes of clusters of different atomic compositions.

Anomalous small-angle scattering as a way to solve the Babinet principle problem

NASA Astrophysics Data System (ADS)

Boiko, M. E.; Sharkov, M. D.; Boiko, A. M.; Bobyl, A. V.

2013-12-01

X-ray absorption spectra (XAS) have been used to determine the absorption edges of atoms present in a sample under study. A series of small-angle X-ray scattering (SAXS) measurements using different monochromatic X-ray beams at different wavelengths near the absorption edges is performed to solve the Babinet principle problem. The sizes of clusters containing atoms determined by the method of XAS were defined in SAXS experiments. In contrast to differential X-ray porosimetry, anomalous SAXS makes it possible to determine sizes of clusters of different atomic compositions.

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

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

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

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

Mullite and Mullite Ceramics

DTIC Science & Technology

1994-01-01

possible. The here reported measurements were carried out with synchrotron radiation from the electron storage ring ELSA of the Bonn University. All...Physikalisches Institut der Universitdt Bonn , Bonn , Germany Measurements of X-ray absorption spectra near the absorption edge of a selected element (XANES

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

NASA Astrophysics Data System (ADS)

Livins, Peteris

1998-10-01

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

Effect of X-ray irradiation on the optical absorption of СdSe1-xTex nanocrystals embedded in borosilicate glass

NASA Astrophysics Data System (ADS)

Prymak, M. V.; Azhniuk, Yu. M.; Solomon, A. M.; Krasilinets, V. M.; Lopushansky, V. V.; Bodnar, I. V.; Gomonnai, A. V.; Zahn, D. R. T.

2012-07-01

The effect of X-ray irradiation on the optical absorption spectra of CdSe1-xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Surface Structure of Aerobically Oxidized Diamond Nanocrystals

DOE PAGES

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

2014-10-27

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

Surface Structure of Aerobically Oxidized Diamond Nanocrystals

PubMed Central

2015-01-01

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

Fast Time-Dependent Density Functional Theory Calculations of the X-ray Absorption Spectroscopy of Large Systems.

PubMed

Besley, Nicholas A

2016-10-11

The computational cost of calculations of K-edge X-ray absorption spectra using time-dependent density functional (TDDFT) within the Tamm-Dancoff approximation is significantly reduced through the introduction of a severe integral screening procedure that includes only integrals that involve the core s basis function of the absorbing atom(s) coupled with a reduced quality numerical quadrature for integrals associated with the exchange and correlation functionals. The memory required for the calculations is reduced through construction of the TDDFT matrix within the absorbing core orbitals excitation space and exploiting further truncation of the virtual orbital space. The resulting method, denoted fTDDFTs, leads to much faster calculations and makes the study of large systems tractable. The capability of the method is demonstrated through calculations of the X-ray absorption spectra at the carbon K-edge of chlorophyll a, C 60 and C 70 .

Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

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

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-30

Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexesmore » in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.« less

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.

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

PubMed

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

2008-04-17

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

Fermi-Edge Singularity of Spin-Polarized Electrons

NASA Astrophysics Data System (ADS)

Plochocka-Polack, P.; Groshaus, J. G.; Rappaport, M.; Umansky, V.; Gallais, Y.; Pinczuk, A.; Bar-Joseph, I.

2007-05-01

We study the absorption spectrum of a two-dimensional electron gas (2DEG) in a magnetic field. We find that at low temperatures, when the 2DEG is spin polarized, the absorption spectra, which correspond to the creation of spin up or spin down electrons, differ in magnitude, linewidth, and filling factor dependence. We show that these differences can be explained as resulting from the creation of a Mahan exciton in one case, and of a power law Fermi-edge singularity in the other.

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

NASA Astrophysics Data System (ADS)

Grein, C. H.; John, Sajeev

1990-04-01

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

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

PubMed

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

2005-03-22

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

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

NASA Astrophysics Data System (ADS)

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

2005-03-01

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

Performance of special radiation-hardened optical fibers intended for use in the telecom spectral windows at a megagray level

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

Tomashuk, A.L.; Dianov, E.M.; Golant, K.M.

Gamma-radiation-induced absorption spectra (2.15 MGy(Si)) are compared in N-doped and pure silica fibers fabricated by surface plasma CVD-process under different regimes with the aim to reveal the chief absorption mechanisms in the telecom spectral windows and to work out an optimum fiber design. The long wavelength absorption edge is shown to be the main absorption mechanism at megagray doses. Its value increases with increasing bonded hydrogen concentration in the fiber glass network and is slightly greater in N-doped fibers. No nitrogen-related color centers have been revealed in the short wavelength loss edge, which is determined by chlorine impurity in silica.

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

USGS Publications Warehouse

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

2014-01-01

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

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.

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.

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

PubMed

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

2013-04-26

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

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

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

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

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

PubMed Central

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

2017-01-01

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

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

PubMed Central

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

2009-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Detection of significant differences between absorption spectra of neutral helium and low temperature photoionized helium plasmas

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

Bartnik, A.; Wachulak, P.; Fiedorowicz, H.

2013-11-15

In this work, spectral investigations of photoionized He plasmas were performed. The photoionized plasmas were created by irradiation of helium stream, with intense pulses from laser-plasma extreme ultraviolet (EUV) source. The EUV source was based on a double-stream Xe/Ne gas-puff target irradiated with 10 ns/10 J Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region below 20 nm, however, spectrally integrated intensity at longer wavelengths was also significant. The EUV radiation was focused onto a gas stream, injected into a vacuum chamber synchronously with the EUV pulse. The long-wavelength part of the EUVmore » radiation was used for backlighting of the photoionized plasmas to obtain absorption spectra. Both emission and absorption spectra in the EUV range were investigated. Significant differences between absorption spectra acquired for neutral helium and low temperature photoionized plasmas were demonstrated for the first time. Strong increase of intensities and spectral widths of absorption lines, together with a red shift of the K-edge, was shown.« less

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

NASA Astrophysics Data System (ADS)

Kong, Lingzhu; Car, Roberto

2013-03-01

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

Optical response of mixed methylammonium lead iodide and formamidinium tin iodide perovskite thin films

DOE PAGES

Ghimire, Kiran; Zhao, Dewei; Yan, Yanfa; ...

2017-07-13

Here, mixed tin (Sn) and lead (Pb) based perovskite thin films have been prepared by solution processing combining methylammonium lead iodide (MAPbI 3) and formamidinium tin iodide (FASnI 3) precursors. Optical response in the form of complex dielectric function (ε = ε 1 + iε 2) spectra and absorption coefficient (α) spectra of (FASnI 3) 1-x(MAPbI 3) x based perovskite films have been extracted over a spectral range 0.74 to 5.89 eV using spectroscopic ellipsometry. Absorption band edge energy changes as a function of composition for films including FASnI 3, MAPbI 3, and mixed x = 0.20, 0.35, 0.40, andmore » 0.6 (FASnI 3) 1-x(MAPbI 3) x perovskites. (FASnI 3) 0.60(MAPbI 3) 0.4 is found to have the minimum absorption band edge energy near ~1.2 eV.« less

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.

Incorporation of chromium into TiO{sub 2} nanopowders

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

Kollbek, Kamila, E-mail: biernack@agh.edu.pl; AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, Al. Mickiewicza 30, 30-059 Krakow; Sikora, Marcin

2015-04-15

Highlights: • Nanopowders of TiO{sub 2}:Cr with different amount of Cr dopant were obtained by flame spray synthesis, FSS. • Increase in the optical absorption and a shift of the absorption edge were observed upon Cr doping. • HERFD-XANES measurements indicated that the average valence state of titanium ions was preserved. • Increasing magnetic susceptibility of a paramagnetic character was observed upon Cr doping. - Abstract: The paper reports on the results of a study of optical, electronic and magnetic properties of TiO{sub 2} nanopowders doped with Cr ions. Diffused reflectance spectra reveal an increase in the optical absorption andmore » a shift of the absorption edge towards lower energies upon Cr doping. Direct information on the Ti electronic state and the symmetry of its nearest environment is obtained from XANES Ti K-edge spectra. Magnetic behaviour is probed by means of the temperature dependence of DC magnetic susceptibility. Increasing magnetic susceptibility of a paramagnetic character is observed upon increasing chromium doping. The Curie constant of TiO{sub 2}:10 at.% Cr sample (0.12 emu K/mol Oe) is lower than that expected for Cr{sup 3+} (0.1875 emu K/mol Oe) possibly due to the appearance of Cr{sup 4+} or the presence of the orbital contribution to the magnetic moment.« less

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

PubMed Central

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

PubMed

Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

2014-05-29

Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σ p and σ m ). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

Monitoring morphology and hydrogen coverage of nanometric Pt/γ-Al2 O3 particles by in situ HERFD-XANES and quantum simulations.

PubMed

Gorczyca, Agnes; Moizan, Virginie; Chizallet, Celine; Proux, Olivier; Del Net, William; Lahera, Eric; Hazemann, Jean-Louis; Raybaud, Pascal; Joly, Yves

2014-11-10

Platinum nanoclusters highly dispersed on γ-alumina are widely used as heterogeneous catalysts. To understand the chemical interplay between the Pt nanoparticles, the support, and the reductive atmosphere, we performed X-ray absorption near edge structure (XANES) in situ experiments recorded in high energy resolution fluorescence detection (HERFD) mode. Spectra are assigned by comparison with simulated XANES spectra on models obtained by molecular dynamics (DFT-MD). We propose platinum cluster morphologies and quantify the hydrogen coverages compatible with XANES spectra recorded at variable hydrogen pressures and temperatures. Using cutting-edge methodologies to assign XANES spectra, this work gives unequalled atomic insights into the characterization of supported nanoclusters. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

DOE PAGES

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

2017-05-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

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

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

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

2015-05-07

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

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.

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

PubMed

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

2015-12-28

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

Comparative NEXAFS study of the selected icefish hard tissues and hydroxyapatite

NASA Astrophysics Data System (ADS)

Petrova, O. V.; Nekipelov, S. V.; Sivkov, D. V.; Mingaleva, A. E.; Nikolaev, A.; Frank-Kamenetskaya, O. V.; Bazhenov, V. V.; Vyalikh, D. V.; Molodtsov, S. L.; Sivkov, V. N.; Ehrlich, H.

2017-11-01

The structure of native Champsocephalus gunnari icefish otoliths, scales, teeth, bones and pristine hydroxyapatite (HA) were examined using Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. NEXAFS Cls-absorption spectra of the selected icefish hard tissues indicate that otoliths contain anion [CO3]2-. NEXAFS P2p-spectra clearly indicate the absence of phosphorus atoms only within otoliths and scales samples. However, the icefish teeth and bones P2p-spectra demonstrate identical spectral feature typical for the HA. NEXAFS Ca2p-spectra of the icefish hard tissues studied also shows features, which are in good correspondence with HA spectra. Interestingly, there is a red shift ≈ 0.1 eV of the 2p1/2,3/2 → 3d transition energies in NEXAFS Ca2p-spectra of teethes and bones of the C. gunnari in comparison to HA.

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 used to measure its oxidation state despite the very small chemical shifts. We also have taken spectra on the molybdenum M-edges and on the sulfur L-edges of inorganic model compounds.

Near-edge X-ray refraction fine structure microscopy

DOE PAGES

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

2017-02-06

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

X-ray absorption spectra: Graphene, h-BN, and their alloy

NASA Astrophysics Data System (ADS)

Bhowmick, Somnath; Rusz, Jan; Eriksson, Olle

2013-04-01

Using first-principles density functional theory calculations, in conjunction with the Mahan-Nozières-de Dominicis theory, we calculate the x-ray absorption spectra of the alloys of graphene and monolayer hexagonal boron nitride on a Ni (111) substrate. The chemical neighborhood of the constituent atoms (B, C, and N) inside the alloy differs from that of the parent phases. In a systematic way, we capture the change in the K-edge spectral shape, depending on the chemical neighborhood of B, C, and N. Our work also reiterates the importance of the dynamical core-hole screening for a proper description of the x-ray absorption process in sp2-bonded layered materials.

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

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

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

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

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.

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.

Optical and photoconductivity spectra of novel Ag₂In₂SiS₆ and Ag₂In₂GeS₆ chalcogenide crystals.

PubMed

Chmiel, M; Piasecki, M; Myronchuk, G; Lakshminarayana, G; Reshak, Ali H; Parasyuk, O G; Kogut, Yu; Kityk, I V

2012-06-01

Complex spectral studies of near-band gap and photoconductive spectra for novel Ag(2)In(2)SiS(6) and Ag(2)In(2)GeS(6) single crystals are presented. The spectral dependences of photoconductivity clearly show an existence of spectral maxima within the 450 nm-540 nm and 780 nm-920 nm. The fundamental absorption edge is analyzed by Urbach rule. The origin of the spectral photoconductivity spectral maxima is discussed. Temperature dependences of the spectra were done. The obtained spectral features allow to propose the titled crystals as photosensors. An analysis of the absorption and photoconductivity spectra is given within a framework of oversimplified spectroscopic model of complex chalcogenide crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed

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

2007-03-01

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

Local 3d Electronic Structures of Co-Based Complexes with Medicinal Molecules Probed by Soft X-ray Absorption

NASA Astrophysics Data System (ADS)

Yamagami, Kohei; Fujiwara, Hidenori; Imada, Shin; Kadono, Toshiharu; Yamanaka, Keisuke; Muro, Takayuki; Tanaka, Arata; Itai, Takuma; Yoshinari, Nobuto; Konno, Takumi; Sekiyama, Akira

2017-07-01

We have examined the local 3d electronic structures of Co-Au multinuclear complexes with the medicinal molecules d-penicillaminate (d-pen) [Co{Au(PPh3)(d-pen)}2]ClO4 and [Co3{Au3(tdme)(d-pen)3}2] by Co L2,3-edge soft X-ray absorption (XAS) spectroscopy, where PPh3 denotes triphenylphosphine and tdme stands for 1,1,1-tris[(diphenylphosphino)methyl]ethane. The Co L2,3-edge XAS spectra indicate the localized ionic 3d electronic states in both materials. The experimental spectra are well explained by spectral simulation for a localized Co ion under ligand fields with the full multiplet theory, which verifies that the ions are in the low-spin Co3+ state in the former compound and in the high-spin Co2+ state in the latter.

Influence of oxygen on growth of carbon thin films

NASA Astrophysics Data System (ADS)

Kumar, Prabhat; Gupta, Mukul; Phase, D. M.; Stahn, Jochen

2018-04-01

In this work we studied the influence of oxygen gas on growth of carbon thin films in a magnetron sputtering process. X-ray absorption spectroscopy (XAS), x-ray and neutron reflectivity techniques were used to probe carbon thin films deposited with and without oxygen at room temperature. XAS in particularly x-ray absorption near edge spectroscopy (XANES) is powerful technique to identify the nature of hybridization of carbon atoms with other elements. In a XANES pattern, presence of C=O and C-O bonds is generally observed in spite of the fact that oxygen has not been deliberately included in the growth process. In order to confirm the presence of such features, we introduced a small amount of oxygen at 1% during the growth of carbon thin films. Though such additions do not affect the number density as observed by x-ray and neutron reflectivity, they severally affect the C K-edge spectra as evidenced by an enhancement in carbon-oxygen hybridization. Observed results are helpful in analyzing the C K-edge spectra more confidently.

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

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE PAGES

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis; ...

2016-12-30

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

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

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

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

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.

An X-ray absorption spectroscopic study of the metal site preference in Al1-xGaxFeO3

NASA Astrophysics Data System (ADS)

Walker, James D. S.; Grosvenor, Andrew P.

2013-01-01

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO3 (Pna21; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al1-xGaxFeO3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L2,3-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al1-xGaxFeO3 indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO3 than in GaFeO3, implying more anti-site disorder is present in AlFeO3.

Theoretical study of nitrogen-doped graphene nanoflakes: Stability and spectroscopy depending on dopant types and flake sizes.

PubMed

Lin, Chih-Kai

2018-03-05

As nitrogen-doped graphene has been widely applied in optoelectronic devices and catalytic reactions, in this work we have investigated where the nitrogen atoms tend to reside in the material and how they affect the electron density and spectroscopic properties from a theoretical point of view. DFT calculations on N-doped hexagonal and rectangular graphene nanoflakes (GNFs) showed that nitrogen atoms locating on zigzag edges are obviously more stable than those on armchair edges or inside flakes, and interestingly, the N-hydrogenated pyridine moiety could be preferable to pure pyridine moiety in large models. The UV-vis absorption spectra of these nitrogen-doped GNFs display strong dependence on flake sizes, where the larger flakes have their major peaks in lower energy ranges. Moreover, the spectra exhibit different connections to various dopant types and positions: the graphitic-type dopant species present large variety in absorption profiles, while the pyridinic-type ones show extraordinary uniform stability and spectra independent of dopant positions/numbers and hence are hardly distinguishable from each other. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

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

PubMed Central

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

2013-01-01

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

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

PubMed

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

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time. Electronic supplementary information (ESI) available: The deconvoluted reference spectra are given in ESI Fig. 1-9. See DOI: 10.1039/c4nr07051h

Electroluminescence in CdSe/PVA nanocomposites

NASA Astrophysics Data System (ADS)

Kumari, Sarita; Ramrakhiani, M.; Khare, P. K.

2018-05-01

The synthesis of II-VI nanocrystal into the polymer matrix to form nanocomposites with adjustable nanocrystal is of great interest size is a big challenge to the scientific community. In present work semiconducting CdSe/PVA thin film were synthesized by single step solution method with different concentration of CdSe. The as-prepared products were characterized by UV-Visible absorption spectra and FESEM. Absorption spectra of CdSe/PVA nanocomposites indicated that the position of absorption edge shifts to smaller wavelength by increasing the concentration of CdSe. For Electroluminescence a turn on voltage is required for light emission and brightness increases with voltage. Turn on voltage is found to decrease as CdSe concentration is increased. The voltage-current curve represents ohmic nature for all EL cells.

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.

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

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

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

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

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

DOE PAGES

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

2017-05-30

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

Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

NASA Astrophysics Data System (ADS)

Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

2018-06-01

Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

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

DOE PAGES

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

2016-06-30

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

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3-micrometers Region: Role of Periphery

NASA Technical Reports Server (NTRS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2017-01-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3-micrometers absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 per cm range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3-micrometers region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3-micrometers band, and on features such as the two-component emission character of this band and the 3-micrometers emission plateau.

High-resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3 μm Region: Role of Periphery

NASA Astrophysics Data System (ADS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

Ultra-violet and visible absorption characterization of explosives by differential reflectometry.

PubMed

Dubroca, Thierry; Moyant, Kyle; Hummel, Rolf E

2013-03-15

This study presents some optical properties of TNT (2,4,6-trinitrotoluene), RDX, HMX and tetryl, specifically their absorption spectra as a function of concentration in various solvents in the ultraviolet and visible portion of the electromagnetic spectrum. We utilize a standoff explosives detection method, called differential reflectometry (DR). TNT was diluted in six different solvents (acetone, acetonitrile, ethanol, ethyl acetate, methanol, and toluene), which allowed for a direct comparison of absorption features over a wide range of concentrations. A line-shape analysis was adopted with great accuracy (R(2)>0.99) to model the absorption features of TNT in differential reflectivity spectra. We observed a blue shift in the pertinent absorption band with decreasing TNT concentration for all solvents. Moreover, using this technique, it was found that for all utilized solvents the concentration of TNT as well as of RDX, HMX, and tetryl, measured as a function of the transition wavelength of the ultra-violet absorption edge in differential reflectivity spectra shows three distinct regions. A model is presented to explain this behavior which is based on intermolecular hydrogen bonding of explosives molecules with themselves (or lack thereof) at different concentrations. Other intermolecular forces such as dipole-dipole interactions, London dispersion forces and π-stacking contribute to slight variations in the resulting spectra, which were determined to be rather insignificant in comparison to hydrogen bonding. The results are aimed towards a better understanding of the DR spectra of explosives energetic materials. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Predicting Near Edge X-ray Absorption Spectra with the Spin-Free Exact-Two-Component Hamiltonian and Orthogonality Constrained Density Functional Theory.

PubMed

Verma, Prakash; Derricotte, Wallace D; Evangelista, Francesco A

2016-01-12

Orthogonality constrained density functional theory (OCDFT) provides near-edge X-ray absorption (NEXAS) spectra of first-row elements within one electronvolt from experimental values. However, with increasing atomic number, scalar relativistic effects become the dominant source of error in a nonrelativistic OCDFT treatment of core-valence excitations. In this work we report a novel implementation of the spin-free exact-two-component (X2C) one-electron treatment of scalar relativistic effects and its combination with a recently developed OCDFT approach to compute a manifold of core-valence excited states. The inclusion of scalar relativistic effects in OCDFT reduces the mean absolute error of second-row elements core-valence excitations from 10.3 to 2.3 eV. For all the excitations considered, the results from X2C calculations are also found to be in excellent agreement with those from low-order spin-free Douglas-Kroll-Hess relativistic Hamiltonians. The X2C-OCDFT NEXAS spectra of three organotitanium complexes (TiCl4, TiCpCl3, TiCp2Cl2) are in very good agreement with unshifted experimental results and show a maximum absolute error of 5-6 eV. In addition, a decomposition of the total transition dipole moment into partial atomic contributions is proposed and applied to analyze the nature of the Ti pre-edge transitions in the three organotitanium complexes.

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

PubMed

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

2014-09-28

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

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

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-03-01

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

Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents

PubMed Central

Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng

2018-01-01

Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively. PMID:29657794

Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents.

PubMed

Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing

2018-03-01

Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.

Low doping concentration studies of doped PVA-Coumarin nanocomposite films

NASA Astrophysics Data System (ADS)

Tripathi, J.; Tripathi, S.; Bisen, R.; Sharma, A.; Choudhary, A.; Shripathi, T.

2016-05-01

The observations of combination of Poly (vinyl) alcohol and Coumarin properties in nanocmposite films are reported. The X-ray diffraction measurements reveal nanocrystalline nature of PVA film, which remains nanocrystalline after doping Coumarin but along with PVA peaks, additional peak due to dopant crystallinity is seen. The absorption edge shows a double edge feature, where distinct bandgaps for PVA host and dopant Coumarin are obtained. However at a higher doping wt % of 1 and 2, the absorption is mainly dominated by Coumarin and single absorption edge is observed giving a bandgap equal to that of bulk Coumarin (3.3 eV). The composite formation affects the bonding of host drastically and is seen through the bond modification in FTIR spectra. The results suggest that doping below 2 wt% is advantageous as combination of PVA and Coumarin properties are obtained but at 2 wt %, the properties are dominated by mainly Coumarin and the signature of PVA from optical properties is completely lost.

Low doping concentration studies of doped PVA-Coumarin nanocomposite films

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

Tripathi, J., E-mail: jtripathi00@rediffmail.com; Bisen, R.; Choudhary, A.

2016-05-23

The observations of combination of Poly (vinyl) alcohol and Coumarin properties in nanocmposite films are reported. The X-ray diffraction measurements reveal nanocrystalline nature of PVA film, which remains nanocrystalline after doping Coumarin but along with PVA peaks, additional peak due to dopant crystallinity is seen. The absorption edge shows a double edge feature, where distinct bandgaps for PVA host and dopant Coumarin are obtained. However at a higher doping wt % of 1 and 2, the absorption is mainly dominated by Coumarin and single absorption edge is observed giving a bandgap equal to that of bulk Coumarin (3.3 eV). Themore » composite formation affects the bonding of host drastically and is seen through the bond modification in FTIR spectra. The results suggest that doping below 2 wt% is advantageous as combination of PVA and Coumarin properties are obtained but at 2 wt %, the properties are dominated by mainly Coumarin and the signature of PVA from optical properties is completely lost.« less

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

PubMed Central

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

Tamura, Tomoyuki; Kohyama, Masanori; Ogata, Shuji

2017-07-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

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

Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

Carbon X-ray absorption in the local ISM: fingerprints in X-ray Novae spectra

NASA Astrophysics Data System (ADS)

Gatuzz, Efraín; Ness, J.-U.; Gorczyca, T. W.; Hasoglu, M. F.; Kallman, Timothy R.; García, Javier A.

2018-06-01

We present a study of the C K-edge using high-resolution LETGS Chandra spectra of four novae during their super-soft-source (SSS) phase. We identified absorption lines due to C II Kα, C III Kα and C III Kβ resonances. We used these astronomical observations to perform a benchmarking of the atomic data, which involves wavelength shifts of the resonances and photoionization cross-sections. We used improved atomic data to estimate the C II and C III column densities. The absence of physical shifts for the absorption lines, the consistence of the column densities between multiple observations and the high temperature required for the SSS nova atmosphere modeling support our conclusion about an ISM origin of the respective absorption lines. Assuming a collisional ionization equilibrium plasma the maximum temperature derived from the ratio of C II/C III column densities of the absorbers correspond to Tmax < 3.05 × 104 K.

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.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Optical properties of graphene nanoflakes: Shape matters.

PubMed

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

2016-06-14

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

Optical properties of graphene nanoflakes: Shape matters

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

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

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

Infrared spectroscopic study of the synthetic Mg-Ni talc series

NASA Astrophysics Data System (ADS)

Blanchard, Marc; Méheut, Merlin; Delon, Louise; Poirier, Mathilde; Micoud, Pierre; Le Roux, Christophe; Martin, François

2018-05-01

Five talc samples [(Mg,Ni)3Si4O10(OH)2] covering the entire Mg-Ni solid solution were synthesized following a recently developed and patented process (Dumas et al., Process for preparing a composition comprising synthetic mineral particles and composition, 2013a; Procédé de préparation d'une composition comprenant des particules minérales synthétiques et composition, 2013b), which produces sub-micron talc particles replying to industrial needs. Near- and mid-infrared spectra were collected and compared to infrared spectra modeled from first-principles calculations based on density functional theory. The good agreement between experimental and theoretical spectra allowed assigning unambiguously all absorption bands. We focused in particular on the four main OH stretching bands, which represent good probes of their local physical and chemical environment. The description of the vibrational modes at the origin of these absorption bands and the theoretical determination of absorption coefficients provide a firm basis for quantifying the talc chemical composition from infrared spectroscopy and for discussing the distribution of divalent cations in the octahedral sheet. Results confirm that these synthetic talc samples have a similar structure as natural talc, with a random distribution of Mg and Ni atoms. They only differ from natural talc by their hydrophilic character, which is due to their large proportion of reactive sites on sheet edges due to sub-micronic size of the particles. Therefore, the contribution on infrared spectra of hydroxyls adsorbed on edge sites has also been investigated by computing the infrared signature of hydroxyls of surface models.

Pinned orbital moments in uncompensated antiferromagnetic Co doped ZnO

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

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

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

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

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

DOE PAGES

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

2017-12-12

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

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

PubMed

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

2013-11-18

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

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE 3 μ m REGION: ROLE OF PERIPHERY

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

Maltseva, Elena; Petrignani, Annemieke; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μ m absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm{sup −1} range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μmore » m region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μ m band, and on features such as the two-component emission character of this band and the 3 μ m emission plateau.« less

Randic and Schultz molecular topological indices and their correlation with some X-ray absorption parameters

NASA Astrophysics Data System (ADS)

Khatri, Sunil; Kekre, Pravin A.; Mishra, Ashutosh

2016-10-01

The properties of a molecular system are affected by the topology of molecule. Therefore many studies have been made where the various physic-chemical properties are correlated with the topological indices. These studies have shown a very good correlation demonstrating the utility of the graph theoretical approach. It is, therefore, very natural to expect that the various physical properties obtained by the X-ray absorption spectra may also show correlation with the topological indices. Some complexes were used to establish correlation between topological indices and some X-ray absorption parameters like chemical shift. The chemical shift is on the higher energy side of the metal edge in these complexes. The result obtained in these studies shows that the topological indices of organic molecule acting as a legands can be used for estimating edge shift theoretically.

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

PubMed

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

2013-07-21

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

X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli

PubMed Central

Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef

2013-01-01

Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag+ treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, and dl-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positive S. aureus and Listeria monocytogenes cells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted. PMID:23934494

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.

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

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

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

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

Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view

NASA Astrophysics Data System (ADS)

Prüßmann, T.; Denecke, M. A.; Geist, A.; Rothe, J.; Lindqvist-Reis, P.; Löble, M.; Breher, F.; Batchelor, D. R.; Apostolidis, C.; Walter, O.; Caliebe, W.; Kvashnina, K.; Jorissen, K.; Kas, J. J.; Rehr, J. J.; Vitova, T.

2013-04-01

N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selectivity are not yet well understood. We present systematic comparative near-edge X-ray absorption structure (XANES) spectroscopy investigations at the Gd L3 edge of [GdBTP3](NO3)3, [Gd(BTP)3](OTf)3, Gd(NO3)3, Gd(OTf)3 and N K edge of [Gd(BTP)3](NO3)3, Gd(NO3)3 complexes. The pre-edge absorption resonance in Gd L3 edge high-energy resolution X-ray absorption near edge structure spectra (HR-XANES) is explained as arising from 2p3/2 → 4f/5d electronic transitions by calculations with the FEFF9.5 code. Experimental evidence is found for higher electronic density on Gd in [Gd(BTP)3](NO3)3 and [Gd(BTP)3](OTf)3 compared to Gd in Gd(NO3)3 and Gd(OTf)3, and on N in [Gd(BTP)3](NO3)3 compared to n-Pr-BTP. The origin of the pre-edge structure in the N K edge XANES is explained by density functional theory (DFT) with the ORCA code. Results at the N K edge suggest a change in ligand orbital occupancies and mixing upon complexation but further work is necessary to interpret observed spectral variations.

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

PubMed

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

2016-02-15

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

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

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

2017-01-01

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

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

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

2017-03-01

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

Spectrometric analysis of different fluorophosphate glasses doped with Sm{sup 3+} ions for reddish-orange laser emission

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

Babu, S., E-mail: ratnakaramsvu@gmail.com; Balakrishna, A., E-mail: ratnakaramsvu@gmail.com; Ratnakaram, Y. C., E-mail: ratnakaramsvu@gmail.com

2014-04-24

Optical properties of Sm{sup 3+} doped different fluorophosphate glasses have been synthesized and discussed. The J- O intensity parameters Ω{sub λ} (λ= 2, 4, 6) from absorption spectra have been evaluated. No sharp edges are found in the absorption spectra, which confirm amorphous nature of present glass matrices. Various radiative parameters have been obtained from luminescence spectra for excited states to corresponding {sup 4}G{sub 5/2}→{sup 6}H{sub 5/2}, {sup 6}H{sub 7/2}, {sup 6}H{sub 9/2} and {sup 6}H{sub 11/2} transitions. The nature of decay curve analysis was performed for the {sup 4}G{sub 5/2} level. These glasses are expected to give interesting applicationmore » in field of optical devices.« less

Site partitioning of Cr3+ in the trichroic alexandrite BeAl2O4:Cr3+ crystal: contribution from x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Bordage, Amélie; Rossano, Stéphanie; Horn, Adolf Heinrich; Fuchs, Yves

2012-06-01

X-ray absorption spectroscopy measurements at the Cr K-edge of a trichroic crystal of alexandrite BeAl2O4:Cr3+ for different orientations of the crystal with respect to the polarization and direction of the x-ray incident beam have been performed. Analysis of the experimental spectra with the help of first-principles calculations of x-ray absorption spectra allowed us to estimate the proportion of chromium Cr3+ cations among the two different octahedral sites of the alexandrite structure (70% in the Cs site-30% in the Ci site). The methodology presented in this work opens up new possibilities in the field of mineralogy for the study of complex minerals containing several sites potentially occupied by several transition elements or for solid solutions.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Electronic structure and x-ray spectroscopy of Cu2MnAl1-xGax

NASA Astrophysics Data System (ADS)

Rai, D. P.; Ekuma, C. E.; Boochani, A.; Solaymani, S.; Thapa, R. K.

2018-04-01

We explore the electronic and related properties of Cu2MnAl1-xGax with a first-principles, relativistic multiscattering Green function approach. We discuss our results in relation to existing experimental data and show that the electron-core hole interaction is essential for the description of the optical spectra especially in describing the X-ray absorption and magnetic circular dichroism spectra at the L2,3 edges of Cu and Mn.

Resonant inelastic x-ray scattering and UV-VUV luminescence at the Be 1s edge in BeO.

PubMed

Kikas, A; Käämbre, T; Kooser, K; Kuusik, I; Kisand, V; Nõmmiste, E; Kirm, M; Feldbach, E; Ivanov, V; Pustovarov, V; Martinson, I

2010-09-22

We carried out a combined study of UV-VUV luminescence and resonant x-ray emission from BeO single crystals with incident photon energies in the vicinity of the Be 1s absorption edge. The x-ray emission spectra show that at the Be 1s photoabsorption edge the lattice relaxation processes in the excitation site take place already on the timescale of the radiative decay of the core excitation. Comparison of the x-ray emission and the luminescence spectra indicates that the maximum energy loss of the process of lattice relaxation during the decay of inner-shell holes is similar to the loss that occurs in the self-trapping process of valence excitons. The possible decay channels of core excitations have been discussed and the mechanism for the creation of 5.2 eV luminescence at the photoabsorption resonances has been suggested.

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.

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

NASA Astrophysics Data System (ADS)

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

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

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.

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.

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.

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

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

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

2016-04-04

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

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

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

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

2008-04-15

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

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

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

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

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

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

DOE PAGES

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

2016-11-30

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

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

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

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

2010-12-03

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

Temperature studies of optical parameters of (Ag3AsS3)0.6(As2S3)0.4 thin films prepared by rapid thermal evaporation and pulse laser deposition

NASA Astrophysics Data System (ADS)

Studenyak, I. P.; Kutsyk, M. M.; Buchuk, M. Yu.; Rati, Y. Y.; Neimet, Yu. Yu.; Izai, V. Yu.; Kökényesi, S.; Nemec, P.

2016-02-01

(Ag3AsS3)0.6(As2S3)0.4 thin films were deposited using rapid thermal evaporation (RTE) and pulse laser deposition (PLD) techniques. Ag-enriched micrometre-sized cones (RTE) and bubbles (PLD) were observed on the thin film surface. Optical transmission spectra of the thin films were studied in the temperature range 77-300 K. The Urbach behaviour of the optical absorption edge in the thin films due to strong electron-phonon interaction was observed, the main parameters of the Urbach absorption edge were determined. Temperature dependences of the energy position of the exponential absorption edge and the Urbach energy are well described in the Einstein model. Dispersion and temperature dependences of refractive indices were analysed; a non-linear increase of the refractive indices with temperature was revealed. Disordering processes in the thin films were studied and compared with bulk composites, the differences between the thin films prepared by RTE and PLD were analysed.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Far Ultraviolet Spectroscopy of Saturn's Icy Moon Rhea

NASA Astrophysics Data System (ADS)

Elowitz, Mark; Hendrix, Amanda; Mason, Nigel J.; Sivaraman, Bhalamurugan

2018-01-01

We present an analysis of spatially resolved, far-UV reflectance spectra of Saturn’s icy satellite Rhea, collected by the Cassini Ultraviolet Imaging Spectrograph (UVIS). In recent years ultraviolet spectroscopy has become an important tool for analysing the icy satellites of the outer solar system (1Hendrix & Hansen, 2008). Far-UV spectroscopy provides unique information about the molecular structure and electronic transitions of chemical species. Many molecules that are suspected to be present in the icy surfaces of moons in the outer solar system have broad absorption features due to electronic transitions that occur in the far-UV portion of the spectrum. The studies show that Rhea, like the other icy satellites of the Saturnian system are dominated by water-ice as evident by the 165-nm absorption edge, with minor UV absorbing contaminants. Far-UV spectra of several Saturnian icy satellites, including Rhea and Dione, show an unexplained weak absorption feature centered near 184 nm. To carry out the geochemical survey of Rhea’s surface, the UVIS observations are compared with vacuum-UV spectra of thin-ice samples measured in laboratory experiments. Thin film laboratory spectra of water-ice and other molecular compounds in the solid phase were collected at near-vacuum conditions and temperatures identical to those at the surface of Rhea. Comparison between the observed far-UV spectra of Rhea’s surface ice and modelled spectra based on laboratory absorption measurements of different non-water-ice compounds show that two possible chemical compounds could explain the 184-nm absorption feature. The two molecular compounds include simple chlorine molecules and hydrazine monohydrate. Attempts to explain the source(s) of these compounds on Rhea and the scientific implications of their possible discovery will be summarized.[1] Hendrix, A. R. & Hansen, C. J. (2008). Icarus, 193, pp. 323-333.

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

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

Vjunov, Aleksei; Wang, Meng; Govind, Niranjan

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

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

First principles study of electronic properties, interband transitions and electron energy loss of α-graphyne

NASA Astrophysics Data System (ADS)

Behzad, Somayeh

2016-04-01

The electronic and optical properties of α-graphyne sheet are investigated by using density functional theory. The results confirm that α-graphyne sheet is a zero-gap semimetal. The optical properties of the α-graphyne sheet such as dielectric function, refraction index, electron energy loss function, reflectivity, absorption coefficient and extinction index are calculated for both parallel and perpendicular electric field polarizations. The optical spectra are strongly anisotropic along these two polarizations. For (E ∥ x), absorption edge is at 0 eV, while there is no absorption below 8 eV for (E ∥ z).

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

PubMed

Chantler, C T; Bourke, J D

2014-04-09

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

Room-Temperature Coherent Optical Phonon in 2D Electronic Spectra of CH 3NH 3PbI 3 Perovskite as a Possible Cooling Bottleneck

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

Monahan, Daniele M.; Guo, Liang; Lin, Jia

2017-06-29

A hot phonon bottleneck may be responsible for slow hot carrier cooling in methylammonium lead iodide hybrid perovskite, creating the potential for more efficient hot carrier photovoltaics. In room-temperature 2D electronic spectra near the band edge, we observe in this paper amplitude oscillations due to a remarkably long lived 0.9 THz coherent phonon population at room temperature. This phonon (or set of phonons) is assigned to angular distortions of the Pb–I lattice, not coupled to cation rotations. The strong coupling between the electronic transition and the 0.9 THz mode(s), together with relative isolation from other phonon modes, makes it likelymore » to cause a phonon bottleneck. Finally, the pump frequency resolution of the 2D spectra also enables independent observation of photoinduced absorptions and bleaches independently and confirms that features due to band gap renormalization are longer-lived than in transient absorption spectra.« less

Characterization of Infrared Properties of Layered Semiconductors.

DTIC Science & Technology

1987-02-20

candidate -10- V. PUBLICATIONS INCLUDED WITH REPORT 1) R. Braunstein, R. K . Kim, D. Matthews, and M. Braunstein: "Derivative Absorption Spectroscopy of...34Wavelength Modulation Spectra of a-Ag0.7Zn0 .3 Near the Optical Absorption Edge," Phys. Stat. Sol.(b) 131, 659 (1983). 5) R. K . Kim and R. Braunstein...34Infrared Wavelength Modulation Spectroscopy of Some Optical Material," Appl. Optics 23(8), 1166 (1984). 6) C.E. Jones, K . James, J. Merz, R. Braunstein, M

X-Ray Absorption Spectroscopy As a Probe of Microbial Sulfur Biochemistry: the Nature of Bacterial Sulfur Globules Revisited

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

George, G.N.; Gnida, M.; Bazylinski, D.A.

2009-05-18

The chemical nature of the sulfur in bacterial sulfur globules has been the subject of controversy for a number of years. Sulfur K-edge X-ray absorption spectroscopy (XAS) is a powerful technique for probing the chemical forms of sulfur in situ, but two groups have used it with very different conclusions. The root of the controversy lies with the different detection strategies used by the two groups, which result in very different spectra. This paper seeks to resolve the controversy. We experimentally demonstrate that the use of transmittance detection for sulfur K-edge XAS measurements is highly prone to spectroscopic distortions andmore » that much of the published work on sulfur bacteria is very likely based on distorted data. We also demonstrate that all three detection methods used for X-ray absorption experiments yield essentially identical spectra when the measurements are carried out under conditions where no experimental distortions are expected. Finally, we turn to the original question--the chemical nature of bacterial sulfur. We examine isolated sulfur globules of Allochromatium vinosum and intact cells of a strain of magnetotactic coccus and show that XAS indicates the presence of a chemical form of sulfur resembling S{sub 8}.« less

Experimental and theoretical study of the structural environment of magnesium in minerals and silicate glasses using X-ray absorption near-edge structure

NASA Astrophysics Data System (ADS)

Trcera, Nicolas; Cabaret, Delphine; Rossano, Stéphanie; Farges, François; Flank, Anne-Marie; Lagarde, Pierre

2009-05-01

X-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

Quasiparticle Lifetime Broadening in Resonant X-ray Scattering of NH4NO3.

PubMed

Vinson, John; Jach, Terrence; Müller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

2016-07-15

It has been previously shown that two effects cause dramatic changes in the x-ray absorption and emission spectra from the N K edge of the insulating crystal ammonium nitrate. First, vibrational disorder causes major changes in the absorption spectrum, originating not only from the thermal population of phonons, but, significantly, from zero-point motion as well. Second, the anomalously large broadening ( ~ 4 eV) of the emission originating from nitrate σ states is due to unusually short lifetimes of quasiparticles in an otherwise extremely narrow band. In this work we investigate the coupling of these effects to core and valence excitons that are created as the initial x-ray excitation energy is progressively reduced toward the N edge. Using a GW /Bethe-Salpeter approach, we show the extent to which this anomalous broadening is captured by the GW approximation. The data and calculations demonstrate the importance that the complex self-energies (finite lifetimes) of valence bands have on the interpretation of emission spectra. We produce a scheme to explain why extreme lifetimes should appear in σ states of other similar compounds.

Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles.

PubMed

Nilsson, Hans J; Tyliszczak, Tolek; Wilson, Richard E; Werme, Lars; Shuh, David K

2005-09-01

A descriptive account is given of our most recent research on the actinide dioxides with the Advanced Light Source Molecular Environmental Science (ALS-MES) Beamline 11.0.2 soft X-ray scanning transmission X-ray microscope (STXM) at the Lawrence Berkeley National Laboratory (LBNL). The ALS-MES STXM permits near-edge X-ray absorption fine structure (NEXAFS) and imaging with 30-nm spatial resolution. The first STXM spectromicroscopy NEXAFS spectra at the actinide 4d5/2 edges of the imaged transuranic particles, NpO2 and PuO2, have been obtained. Radiation damage induced by the STXM was observed in the investigation of a mixed oxidation state particle (Np(V,VI)) and was minimized during collection of the actual spectra at the 4d5/2 edge of the Np(V,VI) solid. A plutonium elemental map was obtained from an irregular PuO2 particle with the dimensions of 650 x 650 nm. The Pu 4d5/2 NEXAFS spectra were collected at several different locations from the PuO2 particle and were identical. A representative oxygen K-edge spectrum from UO2 was collected and resembles the oxygen K-edge from the bulk material. The unique and current performance of the ALS-MES STXM at extremely low energies (ca. 100 eV) that may permit the successful measurement of the actinide 5d edge is documented. Finally, the potential of STXM as a tool for actinide investigations is briefly discussed.

Leaf absorbance and photosynthesis

NASA Technical Reports Server (NTRS)

Schurer, Kees

1994-01-01

The absorption spectrum of a leaf is often thought to contain some clues to the photosynthetic action spectrum of chlorophyll. Of course, absorption of photons is needed for photosynthesis, but the reverse, photosynthesis when there is absorption, is not necessarily true. As a check on the existence of absorption limits we measured spectra for a few different leaves. Two techniques for measuring absorption have been used, viz. the separate determination of the diffuse reflectance and the diffuse transmittance with the leaf at a port of an integrating sphere and the direct determination of the non-absorbed fraction with the leaf in the sphere. In a cross-check both methods yielded the same results for the absorption spectrum. The spectrum of a Fuchsia leaf, covering the short-wave region from 350 to 2500 nm, shows a high absorption in UV, blue and red, the well known dip in the green and a steep fall-off at 700 nm. Absorption drops to virtually zero in the near infrared, with subsequent absorptions, corresponding to the water absorption bands. In more detailed spectra, taken at 5 nm intervals with a 5 nm bandwidth, differences in chlorophyll content show in the different depths of the dip around 550 nm and in a small shift of the absorption edge at 700 nm. Spectra for Geranium (Pelargonium zonale) and Hibiscus (with a higher chlorophyll content) show that the upper limit for photosynthesis can not be much above 700 nm. No evidence, however, is to be seen of a lower limit for photosynthesis and, in fact, some experiments down to 300 nm still did not show a decrease of the absorption although it is well recognized that no photosynthesis results with 300 nm wavelengths.

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.

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.

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

NASA Astrophysics Data System (ADS)

Arzumanyan, Grigory M.; Kuznetsov, Evgeny A.; Zhilin, Aleksandr A.; Dymshits, Olga S.; Shemchuk, Daria V.; Alekseeva, Irina P.; Mudryi, Alexandr V.; Zhivulko, Vadim D.; Borodavchenko, Olga M.

2016-12-01

Glasses of the K2Osbnd ZnOsbnd Al2O3sbnd SiO2 system co-doped with Eu2O3 and Yb2O3 were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass-ceramics were obtained by secondary heat-treatments at 680-860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu3+ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu3+ ions dominated by the 5D0-7F2 (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu3+-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400-850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.

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.

Optical characteristics of butyl rubber loaded with general purpose furnace (GPF) carbon black

NASA Astrophysics Data System (ADS)

Alfaramawi, K.

2018-06-01

Optical characteristics of butyl rubber/GPF carbon black (BR/GPFCB) composites with carbon black (CB) concentrations 40, 60, 80 and 100 phr (part per hundred part of rubber) were investigated. The structure of the BR/GPFCB composites was analyzed by x-ray diffraction (XRD). All samples with various CB showed diffraction peaks around 2θ = 14°, 25° and 44° which correspond to interlayer spacing of 6.23 Å, 3.62 Å and 2.10 Å respectively. The peaks were shifted toward larger 2θ angles with increasing CB concentration, indicating a decrease in layer spacing. Ultraviolet and visible (UV–vis) absorbance spectra in the range from 200 nm to 800 nm of the BR/GPFCB composites were studied. In the UV range of the spectra, an absorption edge was recorded. Direct and indirect optical band gaps for the composites were evaluated. The direct band gap values were found-as shown to be slightly greater than that of the indirect ones. The reflectance spectra in the UV optical range were demonstrated. Most of the incident UV light was absorbed inside the composites while a very small fraction was reflected and transmitted. This was attributed to the high UV absorption property of the CB filler. The refractive index of the composite was calculated from the reflectance data. The dependence of the real and imaginary parts of the complex dielectric constant on the incident light energy was characterized. The dielectric loss factor was found to decrease with increasing incident photon energy until approximately 5.5 eV (around the absorption edge) and then it increased rapidly.

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

PubMed

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

2007-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Accretion disk modeling of AGN continuum using non-LTE stellar atmospheres. [active galactic nuclei (AGN)

NASA Technical Reports Server (NTRS)

Sun, Wei-Hsin; Malkan, Matthew A.

1988-01-01

Active galactic nuclei (AGN) accretion disk spectra were calculated using non-LTE stellar atmosphere models for Kerr and Schwarzschild geometries. It is found that the Lyman limit absorption edge, probably the most conclusive observational evidence for the accretion disk, would be drastically distorted and displaced by the relativistic effects from the large gravitational field of the central black hole and strong Doppler motion of emitting material on the disk surface. These effects are especially pronounced in the Kerr geometry. The strength of the Lyman limit absorption is very sensitive to the surface gravity in the stellar atmosphere models used. For models at the same temperature but different surface gravities, the strength of the Lyman edge exhibits an almost exponential decrease as the surface gravity approach the Eddington limit, which should approximate the thin disk atmosphere. The relativistic effects as well as the vanishing of the Lyman edge at the Eddington gravity may be the reasons that not many Lyman edges in the rest frames of AGNs and quasars are found.

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

NASA Astrophysics Data System (ADS)

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

2006-11-01

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

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

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

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

X-ray Raman scattering for structural investigation of silica/silicate minerals

NASA Astrophysics Data System (ADS)

Fukui, H.; Kanzaki, M.; Hiraoka, N.; Cai, Y. Q.

2009-03-01

We have performed X-ray Raman scattering (XRS) measurements on the oxygen K and silicon L absorption edges of four silica minerals: α-quartz, α-cristobalite, coesite, and stishovite. We have also calculated the partial electron densities of states (DOSs) and compared these with the XRS spectra. This study demonstrates that the short-range structure around the atom of interest strongly influences the XRS spectral features. Importantly, the oxygen K-edge XRS spectra are found to reflect the p-orbital DOS while the silicon L-edge spectra reflect the s- and d-orbital DOSs, even when a product of a momentum transfer and a mean radius of a electron orbit (1 s for oxygen and 2 p for silicon), Qr, is close to or larger than unity. Building on this, calculations of the partial DOSs for other silica phases are presented, including ultra-high-pressure phases, which provide a good reference for further XRS study of silica and silicate minerals. XRS measurements should be performed on not only either of oxygen or silicon but also on many kinds of constituent elements to reveal the structural change of glasses/melts of silicates under extreme conditions.

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

PubMed

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

2015-03-18

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

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

PubMed

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

2013-01-16

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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.

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

Polarization-Dependent Ti 2p-Resonant X-ray Raman Scattering from Ti2O3

NASA Astrophysics Data System (ADS)

Tezuka, Yasuhisa; Nakajima, Nobuo; Adachi, Jun-ichi; Morimoto, Osamu; Sato, Hitoshi; Uozumi, Takayuki

2017-12-01

Detailed resonant X-ray emission spectra (XES) and these polarization dependences of Ti2O3 were obtained by excitation at the Ti 2p absorption edge. About 100 XES spectra were observed in different polarization configurations. X-ray Raman scattering spectra showed two types of crystal field (dd) excitations as well as charge-transfer (CT) excitations. Bulk states of the powder sample were obtained by the XES measurement, which is the photon-in/photon-out method. Partial photon yields (PPYs) of some elementary excitations were extracted from the XES spectra. The CT excitations were hidden in total electron yield spectra, but these were revealed by PPY measurements. Symmetry information of these excitations was acquired on the basis of polarization dependences.

Optimizing soft X-ray NEXAFS spectroscopy in the laboratory

NASA Astrophysics Data System (ADS)

Mantouvalou, I.; Jonas, A.; Witte, K.; Jung, R.; Stiel, H.; Kanngießer, B.

2017-05-01

Near edge X-ray absorption fine structure (NEXAFS) spectroscopy in the soft X-ray range is feasible in the laboratory using laser-produced plasma sources. We present a study using seven different target materials for optimized data analysis. The emission spectra of the materials with atomic numbers ranging from Z = 6 to Z = 79 show distinct differences, rendering the adapted selection of a suitable target material for specialized experiments feasible. For NEXAFS spectroscopy a 112.5 nm thick polyimide film is investigated as a reference exemplifying the superiority of quasi-continuum like emission spectra.

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 appropriate exposure techniques for a series of end point energies from 25 to 35 kVp. The average difference between the kVp determination and the calibrated dial setting was 0.8 and 1.0 kV for a Senographe 600 T and a Senographe DMR, respectively. Since the k-edge absorption energies of the filter materials are well known, independent calibration or a series of calibration curves is not required.

DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

PubMed

Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

2013-01-01

Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2).

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

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

2009-11-01

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

CaCl 2 -Accelerated Hydration of Tricalcium Silicate: A STXM Study Combined with 29 Si MAS NMR

DOE PAGES

Li, Qinfei; Ge, Yong; Geng, Guoqing; ...

2015-01-01

Tmore » he effect of calcium chloride (CaCl 2 ) on tricalcium silicate (C 3 S) hydration was investigated by scanning transmission X-ray microscopy (SXM) with Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra and 29 Si MAS NMR. SXM is demonstrated to be a powerful tool for studying the chemical composition of a cement-based hydration system. he Ca L 3,2 -edge NEXAFS spectra obtained by examining C 3 S hydration in the presence of CaCl 2 showed that this accelerator does not change the coordination of calcium in the calcium silicate hydrate (C-S-H), which is the primary hydration product. O K-edge NEXAFS is also very useful in distinguishing the chemical components in hydrated C 3 S. Based on the Ca L 3,2 -edge spectra and chemical component mapping, we concluded that CaCl 2 prefers to coexist with unhydrated C 3 S instead of C-S-H. In Si K-edge NEXAFS analysis, CaCl 2 increases the degree of silicate polymerization of C-S-H in agreement with the 29 Si CP/MAS NMR results, which show that the presence of CaCl 2 in hydrated C 3 S considerably accelerates the formation of middle groups ( Q 2 ) and branch sites ( Q 3 ) in the silicate chains of C-S-H gel at 1-day hydration.« less

Effects of Na Doping on Structural, Optical, and Electronic Properties of ZnO Thin Films Fabricated by Sol-Gel Technique

NASA Astrophysics Data System (ADS)

Fan, Heliang; Yao, Zhen; Xu, Cheng; Wang, Xinqiang; Yu, Zhichao

2018-04-01

Undoped and Na-doped ZnO thin films were fabricated by sol-gel technique on quartz glass substrates and annealed at 500°C for 1 h. The structural properties of the films were characterized using x-ray diffraction analysis, which revealed hexagonal wurtzite structure with no peaks corresponding to Na2O or other Na phases being found. Surface morphology observations by scanning electron microscopy revealed that the crystallite size and topographical properties of the ZnO films were influenced by the Na doping concentration. X-ray photoelectron spectra revealed presence of Na+ in ZnO regime. The transmittance spectra indicated that the average transmittance of Na-doped ZnO film was above 80% in the visible range, superior to that of the undoped film. There was a blue-shift in the ultraviolet absorption edge with increase of the Na content. Photoluminescence spectra illustrated two peaks, corresponding to ultraviolet near-band-edge and visible emission.

EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

NASA Astrophysics Data System (ADS)

De Vicente, F. S.; Santos, F. A.; Simões, B. S.; Dias, S. T.; Siu Li, M.

2014-12-01

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr3+ were studied by Electron Paramagnetic Resonance (EPR), UV-VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr3+-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV-VIS optical absorption spectra of SbPO:Cr3+ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from 4A2(F) to 4T1(F), 4T2(F), 2T1(G), and 2E(G), respectively, of Cr3+ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr3+ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr3+ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr3+ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr3+-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the 3P1 → 1S0 electronic transition from Sb3+ ions. Cr3+-doped glasses excited with 415 nm presented Cr3+ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (2E → 4A2) and another intense band from 700 to 850 nm (4T2 → 4A2).

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

NASA Astrophysics Data System (ADS)

Kumar, Pawan; Pandey, Praveen C.

2018-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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.

Theoretical studies on the structural and spectra properties of two C74 fullerenes and the chlorinated species C74Cl10

NASA Astrophysics Data System (ADS)

Zheng, Mei; Song, Xitong; Li, Xiaoqi; Qi, Jiayuan

2018-07-01

The geometrical/electronic structures, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy of two especially C74 fullerenes (D3h-C74 and C1-C74) and the chlorinated species C1-C74Cl10, which are newly isolated in the experiment, have been calculated by means of the density functional theory (DFT) method. Effective changes in the electronic structure and simulated X-ray spectra have been observed after chlorination. Strong isomer dependence has been found in both spectra, thus the 'fingerprints' in the spectra can be employed as a tool to identify the isomers. The ultraviolet-visible (UV-vis) absorption spectrum of C1-C74Cl10 has been performed by using the time-dependent DFT method. The generated UV-vis spectrum coincides with the previous experimental counterpart. The results of this work can provide useful information especially for isomer identification and further study on fullerenes by means of the aforementioned spectroscopy techniques.

Simultaneous X-ray and Far-Ultraviolet Spectra of AGN with ASCA and HUT

NASA Technical Reports Server (NTRS)

Kriss, Gerard A.

1997-01-01

We obtained ASCA spectra of the Seyfert 1 galaxy NGC 3516 in March 1995. Simultaneous far-UV observations were obtained with the Hopkins Ultraviolet Telescope on the Astro-2 shuttle mission. The ASCA spectrum shows a lightly absorbed power law of energy index 0.78. The low energy absorbing column is significantly less than previously seen. Prominent 0 VII and 0 VIII absorption edges are visible, but, consistent with the much lower total absorbing column, no Fe K absorption edge is detectable. A weak, narrow Fe K(alpha) emission line from cold material is present as well as a broad Fe K(alpha) line. These features are similar to those reported in other Seyfert 1 galaxies. A single warm absorber model provides only an imperfect description of the low energy absorption. In addition to a highly ionized absorber with ionization parameter U = 1.66 and a total column density of 1.4 x 10(exp 22)/sq cm, adding a lower ionization absorber with U = 0.32 and a total column of 6.9 x 10(exp 21)/sq cm significantly improves the fit. The contribution of resonant line scattering to our warm absorber models limits the Doppler parameter to less than 160 km/s at 90% confidence. Turbulence at the sound speed of the photoionized gas provides the best fit. None of the warm absorber models fit to the X-ray spectrum can match the observed equivalent widths of all the UV absorption lines. Accounting for the X-ray and UV absorption simultaneously requires an absorbing region with a broad range of ionization parameters and column densities.

Determination of total x-ray absorption coefficient using non-resonant x-ray emission

PubMed Central

Achkar, A. J.; Regier, T. Z.; Monkman, E. J.; Shen, K. M.; Hawthorn, D. G.

2011-01-01

An alternative measure of x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has recently been developed that is both bulk sensitive and free of saturation effects. Here we show that the angle dependence of IPFY can provide a measure directly proportional to the total x-ray absorption coefficient, µ(E). In contrast, fluorescence yield (FY) and electron yield (EY) spectra are offset and/or distorted from µ(E) by an unknown and difficult to measure amount. Moreover, our measurement can determine µ(E) in absolute units with no free parameters by scaling to µ(E) at the non-resonant emission energy. We demonstrate this technique with measurements on NiO and NdGaO3. Determining µ(E) across edge-steps enables the use of XAS as a non-destructive measure of material composition. In NdGaO3, we also demonstrate the utility of IPFY for insulating samples, where neither EY or FY provide reliable spectra due to sample charging and self-absorption effects, respectively. PMID:22355697

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

PubMed

Asmuruf, Frans A; Besley, Nicholas A

2008-08-14

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Quasiparticle lifetime broadening in resonant x-ray scattering of NH4NO3

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Müller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

2016-07-01

It has been previously shown that two effects cause dramatic changes in the x-ray absorption and emission spectra from the N K edge of the insulating crystal ammonium nitrate. First, vibrational disorder causes major changes in the absorption spectrum, originating not only from the thermal population of phonons, but, significantly, from zero-point motion as well. Second, the anomalously large broadening (˜4 eV) of the emission originating from nitrate σ states is due to the unusually short lifetimes of quasiparticles in an otherwise extremely narrow band. In this work, we investigate the coupling of these effects to core and valence excitons that are created as the initial x-ray excitation energy is progressively reduced toward the N edge. Using a G W /Bethe-Salpeter approach, we show the extent to which this anomalous broadening is captured by the G W approximation. The data and calculations demonstrate the importance that the complex self-energies (finite lifetimes) of the valence bands have on the interpretation of emission spectra. We produce a scheme to explain why extreme lifetimes should appear in σ states of other similar compounds.

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

PubMed

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

2017-02-07

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

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

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

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

Transport, electronic, and structural properties of nanocrystalline CuAlO2 delafossites

NASA Astrophysics Data System (ADS)

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

2011-01-01

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

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

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

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

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

2014-03-28

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

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

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

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

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

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

The remote sensing study of vegetated regions of the world has typically been focused on the use of broad-band vegetation indices such as NDVI. Various modifications of these indices have been developed in attempts to minimize the effect of soil background, e.g., SAVI, or to reduce the effect of the atmosphere, e.g., ARVI. Most of these indices depend on the so-called 'red edge,' the sharp transition between the strong absorption of chlorophyll pigment in visible wavelengths and the strong scattering in the near-infrared from the cellular structure of leaves. These broadband indices tend to become highly inaccurate as the green canopy cover becomes sparse. The advent of high spectral resolution remote sensing instrument such as the Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) has allowed the detection of narrow spectral features in vegetation and there are reports of detection of the red edge even for pixels with very low levels of green vegetation cover by Vane et al. and Elvidge et al., and to characterize algal biomass in coastal areas. Spectral mixing approaches similar to those of Smith et al. can be extended into the high spectral resolution domain allowing for the analysis of more endmembers, and potentially, discrimination between material with narrow spectral differences. Vegetation in arid regions tends to be sparse, often with small leaves such as the creosote bush. Many types of arid region vegetation spend much of the year with their leaves in a senescent state, i.e., yellow, with lowered chlorophyll pigmentation. The sparseness of the leaves of many arid region plants has the dual effect of lowering the green leaf area which can be observed and of allowing more of the sub-shrub soil to be visible which further complicates the spectrum of a region covered with arid region vegetation. Elvidge examined the spectral characteristics of dry plant materials showing significant differences in the region of the red edge and the diagnostic ligno-cellulose absorptions at 2090 nm and 2300 nm. Ray et al. detected absorption at 2100 nm in AVIRIS spectra of an abandoned field known to be covered by a great deal of dead plant litter. In order to better study arid region vegetation remote sensing data, it is necessary to better characterize the reflectance spectra of in situ, living, arid region plants.

Toward understanding as photosynthetic biosignatures: light harvesting and energy transfer calculation

NASA Astrophysics Data System (ADS)

Komatsu, Y.; Umemura, M.; Shoji, M.; Shiraishi, K.; Kayanuma, M.; Yabana, K.

2014-03-01

Among several proposed biosignatures, red edge is a direct evidence of photosynthetic life if it is detected (Kiang et al 2007). Red edge is a sharp change in reflectance spectra of vegetation in NIR region (about 700-750 nm). The sign of red edge is observed by Earthshine or remote sensing (Wolstencroft & Raven 2002, Woolf et al 2002). But, why around 700-750 nm? The photosynthetic organisms on Earth have evolved to optimize the sunlight condition. However, if we consider about photosynthetic organism on extrasolar planets, they should have developed to utilize the spectra of its principal star. Thus, it is not strange even if it shows different vegetation spectra. In this study, we focused on the light absorption mechanism of photosynthetic organisms on Earth and investigated the fundamental properties of the light harvesting mechanisms, which is the first stage for the light absorption. Light harvesting complexes contain photosynthetic pigments like chlorophylls. Effective light absorption and the energy transfer are accomplished by the electronic excitations of collective photosynthetic pigments. In order to investigate this mechanism, we constructed an energy transfer model by using a dipole-dipole approximation for the interactions between electronic excitations. Transition moments and transition energies of each pigment are calculated at the time-dependent density functional theory (TDDFT) level (Marques & Gross 2004). Quantum dynamics simulation for the excitation energy transfer was calculated by the Liouvelle's equation. We adopted the model to purple bacteria, which has been studied experimentally and known to absorb lower energy. It is meaningful to focus on the mechanism of this bacteria, since in the future mission, M planets will become a important target. We calculated the oscillator strengths in one light harvesting complex and confirmed the validity by comparing to the experimental data. This complex is made of an inner and an outer ring. The energy transfer from the outer to the inner ring can be reproduced. To deal with a realistic system, we calculated at a macro structural model. The energy transfer between light harvesting complexes is accomplished rapidly via inner rings. By exchange the original pigment to a pigment absorb lower energy, faster energy transfer occurs and the density was trapped in pigment having lower energy. We will compare the result of purple bacteria, which is considered to show longer red edge, cyanobacteria and plants.

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

PubMed

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

2015-03-01

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

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

PubMed

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

2014-10-14

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

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

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.

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

Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

NASA Astrophysics Data System (ADS)

Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

2016-09-01

The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

S2p core level spectroscopy of short chain oligothiophenes

NASA Astrophysics Data System (ADS)

Baseggio, O.; Toffoli, D.; Stener, M.; Fronzoni, G.; de Simone, M.; Grazioli, C.; Coreno, M.; Guarnaccio, A.; Santagata, A.; D'Auria, M.

2017-12-01

The Near-Edge X-ray-Absorption Fine-Structure (NEXAFS) and X-ray Photoemission Spectroscopy (XPS) of short-chain oligothiophenes (thiophene, 2,2'-bithiophene, and 2,2':5',2″-terthiophene) in the gas phase have been measured in the sulfur L2,3-edge region. The assignment of the spectral features is based on the relativistic two-component zeroth-order regular approximation time dependent density functional theory approach. The calculations allow us to estimate both the contribution of the spin-orbit splitting and of the molecular-field splitting to the sulfur binding energies and give results in good agreement with the experimental measurements. The deconvolution of the calculated S2p NEXAFS spectra into the two manifolds of excited states converging to the LIII and LII edges facilitates the attribution of the spectral structures. The main S2p NEXAFS features are preserved along the series both as concerns the energy positions and the nature of the transitions. This behaviour suggests that the electronic and geometrical environment of the sulfur atom in the three oligomers is relatively unaffected by the increasing chain length. This trend is also observed in the XPS spectra. The relatively simple structure of S2p NEXAFS spectra along the series reflects the localized nature of the virtual states involved in the core excitation process.

Theory of L -edge spectroscopy of strongly correlated systems

NASA Astrophysics Data System (ADS)

Lüder, Johann; Schött, Johan; Brena, Barbara; Haverkort, Maurits W.; Thunström, Patrik; Eriksson, Olle; Sanyal, Biplab; Di Marco, Igor; Kvashnin, Yaroslav O.

2017-12-01

X-ray absorption spectroscopy measured at the L edge of transition metals (TMs) is a powerful element-selective tool providing direct information about the correlation effects in the 3 d states. The theoretical modeling of the 2 p →3 d excitation processes remains to be challenging for contemporary ab initio electronic structure techniques, due to strong core-hole and multiplet effects influencing the spectra. In this work, we present a realization of the method combining the density-functional theory with multiplet ligand field theory, proposed in Haverkort et al. [Phys. Rev. B 85, 165113 (2012), 10.1103/PhysRevB.85.165113]. In this approach, a single-impurity Anderson model (SIAM) is constructed, with almost all parameters obtained from first principles, and then solved to obtain the spectra. In our implementation, we adopt the language of the dynamical mean-field theory and utilize the local density of states and the hybridization function, projected onto TM 3 d states, in order to construct the SIAM. The developed computational scheme is applied to calculate the L -edge spectra for several TM monoxides. A very good agreement between the theory and experiment is found for all studied systems. The effect of core-hole relaxation, hybridization discretization, possible extensions of the method as well as its limitations are discussed.

The effect of thermal reduction on the photoluminescence and electronic structures of graphene oxides.

PubMed

Chuang, C-H; Wang, Y-F; Shao, Y-C; Yeh, Y-C; Wang, D-Y; Chen, C-W; Chiou, J W; Ray, Sekhar C; Pong, W F; Zhang, L; Zhu, J F; Guo, J H

2014-04-10

Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120-180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp(2) bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG.

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

Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J., E-mail: saykally@berkeley.edu

Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopymore » (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.« less

Spectroscopic properties of Er3+-doped fluorotellurite glasses containing various modifiers

NASA Astrophysics Data System (ADS)

Burtan-Gwizdała, Bożena; Reben, Manuela; Cisowski, Jan; Grelowska, Iwona; Yousef, El Sayed; Algarni, Hamed; Lisiecki, Radosław; Nosidlak, Natalia

2017-11-01

We have investigated the optical and spectroscopic properties of new Er3+-doped fluorotellurite glasses with the basic molar composition 75%TeO2-10%P2O5-10%ZnO-5%PbF2, modified by replacing 5%TeO2 by four various metal oxides, namely MgO, PbO, SrO and CdO. The ellipsometric data have provided a Sellmeier-type dispersion relation of the refractive index of the investigated glasses. The optical absorption edge has been described within the Urbach approach, while the absorption and fluorescence spectra have been analyzed in terms of the standard Judd-Ofelt theory along with the photoluminescence decay of the 4I13/2 and 4S3/2 levels of the Er3+ ion. The absorption and emission spectra of the 4I15/2 ↔ 4I13/2 infrared transition have been analyzed within the McCumber theory to yield the peak emission cross-section and figure of merit (FOM) for the amplifier gain. It appears that the glass containing MgO as a modifier is characterized by the largest FOM suggesting that the fluorotellurite matrix with this oxide can be a good novel host for Er3+ ion doping. Finally, we propose a new simple method to calculate the mean transition energy of the McCumber approach as the arithmetic average of the barycenter wavenumbers of absorption and emission spectra.

[Effect of Long-Term Fertilization on Organic Nitrogen Functional Groups in Black Soil as Revealed by Synchrotron-Based X-Ray Absorption Near-Edge Structure Spectroscopy].

PubMed

Li, Hui; Gao, Qiang; Wang, Shuai; Zhu, Ping; Zhang, Jin-jing; Zhao, Yi-dong

2015-07-01

Nitrogen (N) is a common limiting nutrient in crop production. The N content of soil has been used as an important soil fertility index. Organic N is the major form of N in soil. In most agricultural surface soils, more than 90% of total N occurs in organic forms. Therefore, understanding the compositional characteristics of soil organic N functional groups can provide the scientific basis for formulating the reasonable farmland management strategies. Synchrotron radiation soft X-ray absorption near-edge structure (N K-edge XANES) spectroscopy is the most powerful tool to characterize in situ organic N functional groups compositions in soil. However, to our most knowledge, no studies have been conducted to examine the organic N functional groups compositions of soil using N K-edge XANES spectroscopy under long-term fertilization practices. Based on a long-term field experiment (started in 1990) in a black soil (Gongzhuling, Northeast China), we investigated the differences in organic N functional groups compositions in bulk soil and clay-size soil fraction among fertilization patterns using synchrotron-based N K- edge XANES spectroscopy. Composite soil samples (0-20 cm) were collected in 2008. The present study included six treatments: farmland fallow (FALL), no-fertilization control (CK), chemical nitrogen, phosphorus, and potassium fertilization (NPK), NPK in combination with organic manure (NPKM), 1.5 times of NPKM (1.5 NPKM), and NPK in combination with maize straw (NPKS). The results showed that N K-edge XANES spectra of all the treatments under study exhibited characteristic absorption peaks in the ranges of 401.2-401.6 and 402.7-403.1 eV, which were assigned as amides/amine-N and pyrrole-N, respectively. These characteristic absorption peaks were more obvious in clay-size soil fraction than in bulk soil. The results obtained from the semi-quantitative analysis of N K-edge XANES spectra indicated that the relative proportion of amides/amine-N was the highest in both bulk soil and clay-size soil fraction, and it was the most major forms in soil organic nitrogen functional groups. Compared with the FALL treatment, the relative proportion of amide/amine-N was lower whereas that of Pyrrole-N was higher in the CK treatment. In the treatments with combined chemical fertilizers and organic manure, the relative proportion of amide/amine-N decreased with increasing application rates of organic manure, while that of Pyrrole-N had an opposite trend. In bulk soil, the relative proportion of amide/amine-N was the highest for the NPKS treatment than for the other treatments. On the other hand, the relative proportion of nitrile/aromatic-N was the highest for the Fallow treatment than for the other treatments in clay-size soil fraction. It is feasible to use N K-edge XANES spectroscopy for characterizing in situ the changes of organic N functional groups in soil under different fertilization practices.

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

NASA Astrophysics Data System (ADS)

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

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

Singularities in x-ray spectra of metals

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

Mahan, G.D.

1987-08-01

The x-ray spectroscopies discussed are absorption, emission, and photoemission. The singularities show up in each of them in a different manner. In absorption and emission they show up as power law singularities at the thresholds frequencies. This review will emphasize two themes. First a simple model is proposed to describe this phenomena, which is now called the MND model after MAHAN-NOZIERES-DeDOMINICIS. Exact analytical solutions are now available for this model for the three spectroscopies discussed above. These analytical models can be evaluated numerically in a simple way. The second theme of this review is that great care must be usedmore » when comparing the theory to experiment. A number of factors influence the edge shapes in x-ray spectroscopy. The edge singularities play an important role, and are observed in many matals. Quantitative fits of the theory to experiment require the consideration of other factors. 51 refs.« less

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

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.

Determination of band gap in epitaxial delafossite Cu oxide using optical techniques

NASA Astrophysics Data System (ADS)

Cabrera, Alejandro; Wheatley, R.; Seifert, B.; Wallentowitz, S.; Joshi, T.; Lederman, D.

Highly epitaxial delafossite CuFeO2 and CuFe1-xGaxO2 films were grown using Pulsed Laser Deposition techniques. The sample thicknesses were estimated to be 21 nm, 75 nm.The estimated gallium fraction of substituted ferric atoms was x =0.25 for the composite sample. We present the study of the fundamental band gap(s) for each sample via observation of their respective optical absorption properties in the NIR-VIS region using transmittance and diffuse reflection spectroscopy. Predominant absorption edges measured were between 1.1eV and 3.1eV from transmittance spectra. The sample of CuFe1-xGaxO2 showed measurable absorption features located at 2.4eV and 2.8eV. This study also found evidence of changes between apparent absorption edges between transmittance and diffuse reflectance spectroscopies of each sample and it may be resultant from absorption channels via surface states. Future photoluminescence experiments are planned to determine the photo-induced semiconductor behavior of these materials. ACNOWLEDGEMENTS: This work was supported by FONDECyT 1130372 and Proyecto Anillo ACT1409 at PUC and supported in part by the WV Higher Education Policy Commission (Grant HEPC.dsr.12.29) and by FAME sponsored by MARCO and DARPA (contract # 2013-MA-2382).

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

A X-Ray Absorption Study of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Bunker, Grant Byrd

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

Thermal, optical and vibrational studies of tyrosine doped LaF3:Ce nanoparticles for bioimaging and biotagging

NASA Astrophysics Data System (ADS)

Singh, Amit T.

2018-05-01

Upconversion quantum dots of tyrosine doped LaF3:Ce nanoparticles have been synthesized by wet chemical route. The thermal studies (TGA/DTA) confirm the crystallinity and stability of different phases of synthesized nanoparticles. The UV-Visible spectra show multiple absorption edges at 215.60 nm and 243.10 nm indicating quantum dot nature of the synthesized nanoparticles. The PL spectra showed upconversion with sharp emission peak at 615 nm (red colour). The FT-RAMAN spectra of the synthesized nanoparticles show the modification of the surface of the nanoparticles in the form of functional groups and skeletal groups. Upconversion nature of the synthesized nanoparticles indicates their potential application in bioimaging and biotagging.

Hybridized orbital states in spin-orbit coupled 3 d -5 d double perovskites studied by x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Min-Cheol; Lee, Sanghyun; Won, C. J.; Lee, K. D.; Hur, N.; Chen, Jeng-Lung; Cho, Deok-Yong; Noh, T. W.

2018-03-01

We investigated the orbital hybridization mechanism in 3 d -5 d double perovskites (DPs) of La2CoIrO6 and La2CoPtO6 using x-ray absorption spectroscopy. It is clearly evidenced by O K -edge and Co K -edge x-ray absorption spectra that the Co 3 d orbitals hybridize not only with the half-filled Ir/Pt jeff states but also with the fully empty (unpolarized) Ir/Pt eg states in both DPs. The Co 3 d eg-Ir 5 d eg hybridization cannot contribute to the ferrimagnetic long-range order in La2CoIrO6 established by spin-selective Co 3 d t2 g-Ir 5 d jeff hybridization through the intermediate oxygen p state but could serve as an origin of paramagnetism. The strengths of such orbital hybridizations were found to be almost invariant to temperature, even far above the Curie temperature, implying persistent paramagnetism against the antiferromagnetic ordering in the spin-orbit entangled 3 d -5 d DPs.

VOLATILE-RICH CIRCUMSTELLAR GAS IN THE UNUSUAL 49 CETI DEBRIS DISK

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

Roberge, Aki; Grady, Carol A.; Welsh, Barry Y.

2014-11-20

We present Hubble Space Telescope Space Telescope Imaging Spectrograph far-UV spectra of the edge-on disk around 49 Ceti, one of the very few debris disks showing submillimeter CO emission. Many atomic absorption lines are present in the spectra, most of which arise from circumstellar gas lying along the line-of-sight to the central star. We determined the line-of-sight C I column density, estimated the total carbon column density, and set limits on the O I column density. Surprisingly, no line-of-sight CO absorption was seen. We discuss possible explanations for this non-detection, and present preliminary estimates of the carbon abundances in themore » line-of-sight gas. The C/Fe ratio is much greater than the solar value, suggesting that 49 Cet harbors a volatile-rich gas disk similar to that of β Pictoris.« less

An Attosecond Transient Absorption Spectroscopy Setup with a Water Window Attosecond source

NASA Astrophysics Data System (ADS)

Chew, Andrew; Yin, Yanchun; Li, Jie; Ren, Xiaoming; Wang, Yang; Wu, Yi; Chang, Zenghu

2017-04-01

Attosecond transient absorption, or time-resolved pump-probe spectroscopy, are excellent tools that can be used to investigate fast electron dynamics for a given atomic or molecular system. Recent push for high energy long wavelength few cycle laser sources has resulted in the production of x-ray spectra that would allow the probing of electron dynamics at the carbon k-edge in molecules such as CH4 and CO2. The motion of charges can be caused by photo-dissociation and charge migration. We present here the first results from our experimental setup where we produce a broadband attosecond pulse with spectra that stretches into the water window. National Science Foundation (1068604), Army Research Oce (W911NF-14-1-0383), Air Force Oce of Scientic Research (FA9550-15-1-0037, FA9550-16-1-0013) and the DARPA PULSE program by a Grant from AMRDEC (W31P4Q1310017).

Charge transfer transitions in optical spectra of NicMg1-cO oxides

NASA Astrophysics Data System (ADS)

Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Druzhinin, A. V.; Korolyov, A. V.; Kim, G. A.; Zatsepin, A. F.; Kuznetsova, J. A.

2017-04-01

Radiative recombination with charge transfer was observed in NicMg1-cO (c = 0.008) oxides over the 8-300 K temperature range. This recombination occurs as a result of strong hybridization of the Ni2+ ion 3d-states and the band states. The charge transfer radiation excitation spectrum shows vibrational LO repeats of two exciton lines having charge transfer energy intervals of about 35 meV. The NiO nanocrystal absorption spectrum shows two weak peaks with energies of 3.510 and 3.543 eV, which are highly dependent on temperature. They are interpreted as charge transfer excitons at the edge of NiO fundamental absorption. The distance between the charge transfer exciton lines in the NicMg1-cO oxide spectra are caused by spin-orbit splitting of the valence band peak that was formed by the p-states of the oxygen ion.

Excitonic Transitions and Off-resonant Optical Limiting in CdS Quantum Dots Stabilized in a Synthetic Glue Matrix

PubMed Central

2007-01-01

Stable films containing CdS quantum dots of mean size 3.4 nm embedded in a solid host matrix are prepared using a room temperature chemical route of synthesis. CdS/synthetic glue nanocomposites are characterized using high resolution transmission electron microscopy, infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. Significant blue shift from the bulk absorption edge is observed in optical absorption as well as photoacoustic spectra indicating strong quantum confinement. The exciton transitions are better resolved in photoacoustic spectroscopy compared to optical absorption spectroscopy. We assign the first four bands observed in photoacoustic spectroscopy to 1se–1sh, 1pe–1ph, 1de–1dhand 2pe–2phtransitions using a non interacting particle model. Nonlinear absorption studies are done using z-scan technique with nanosecond pulses in the off resonant regime. The origin of optical limiting is predominantly two photon absorption mechanism.

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

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.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell.

PubMed

Hong, Xinguo; Newville, Matthew; Prakapenka, Vitali B; Rivers, Mark L; Sutton, Stephen R

2009-07-01

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within +/-3 degrees relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

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

Hong, X.; Newville, M.; Prakapenka, V.B.

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over amore » small angular range of DAC orientation, e.g., within {+-}3{sup o} relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO{sub 2} recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO{sub 2} glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO{sub 2} glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.« less

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

DOE PAGES

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

2017-02-20

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

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

NASA Astrophysics Data System (ADS)

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

2007-02-01

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

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

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

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

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

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

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

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

2014-06-24

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Electronic Structures and Optical Properties of α-Al2O3Nanowires

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Optical, electrical, thermal properties of cadmium chloride doped PVA – PVP blend

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

Baraker, Basavarajeshwari M.; Hammannavar, Preeti B.; Lobo, Blaise, E-mail: blaise.lobo@gmail.com

2015-06-24

Films of polyvinylalcohol (PVA) – polyvinylpyrrolidone (PVP) blend doped with Cadmium Chloride (CdCl{sub 2}) in the doping range 1 wt% to 40 wt% were prepared by solution casting technique. These films were characterized using optical/UV-Vis- NIR spectroscopy, Differential Scanning Calorimetry (DSC) and DC electrical measurements. The UV-Visible spectra were quantitatively analyzed to yield the optical parameters. The UV-Visible Spectra show intermediate absorption bands (before the final absorption edge) due to formation of energy bands in the forbidden gap of PVA-PVP. There is a prominent absorption band at 2.9 eV, from 0.5 wt% up to 1.8 wt% doping level (DL) causedmore » by the dopant (CdCl{sub 2}). The DC electrical studies showed an increase in activation energy from 2.8 eV at 0.5 wt% DL up to 3.5 eV at 4.4 wt% DL, reaching a low of 2.4 eV at 11.2 wt% DL. DSC scans show evidence of formation of chain fragments, at doping levels beyond 8 wt%.« less

Electronic structure of the La 1 + xBa 2 - xCu 3O 7 + δ system studied by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lindberg, P. A. P.; Shen, Z.-X.; Hwang, J.; Shih, C. K.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Kapitulnik, A.

1989-01-01

Photoemission experiments utilizing synchrotron radiation have been carried out on the high temperature superconductor La 1.075Ba 1.925Cu 3O 7.0. The valence band spectra show similar spectral features as those of YBa 2Cu 3O 6.9, even though large differences in relative peak intensities are observed. Oxygen-related states are identified by scanning the photon energy through the O2 s → O2 p absorption edge. The stability of the sample surface, and changes in the valence band spectra after annealing in ultrahigh vacuum are also briefly discussed.

Band-filling of solution-synthesized CdS nanowires.

PubMed

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

2008-02-01

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

Development of the surface-sensitive soft x-ray absorption fine structure measurement technique for the bulk insulator

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

Yonemura, Takumi, E-mail: yonemura-takumi@sei.co.jp; Iihara, Junji; Uemura, Shigeaki

We have succeeded in measuring X-ray absorption fine structure (TEY-XAFS) spectra of insulating plate samples by total electron yield. The biggest problem is how to suppress the charge-up. We have attempted to deposit a gold stripe electrode on the surface and obtained a TEY-XAFS spectrum. This indicates that the metal stripe electrode is very useful in the TEY-XAFS measurement of the insulating plate samples. In the detailed analysis, we have found that the effective area for suppressing charge-up was approximately 120 μm from the edge of the electrode.

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

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

PubMed

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

2018-03-01

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

The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides

PubMed Central

Chuang, C.-H.; Wang, Y.-F.; Shao, Y.-C.; Yeh, Y.-C.; Wang, D.-Y.; Chen, C.-W.; Chiou, J. W.; Ray, Sekhar C.; Pong, W. F.; Zhang, L.; Zhu, J. F.; Guo, J. H.

2014-01-01

Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120–180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp2 bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG. PMID:24717290

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

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

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

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2014-12-14

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

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.

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

PubMed

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

2014-08-14

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

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

NASA Astrophysics Data System (ADS)

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

2003-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2007-07-01

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

X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

NASA Astrophysics Data System (ADS)

Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

2015-05-01

Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

An experimental study of the local electronic structure of B-site gallium doped bismuth ferrite powders

NASA Astrophysics Data System (ADS)

Gholam, Turghunjan; Ablat, Abduleziz; Mamat, Mamatrishat; Wu, Rong; Aimidula, Aimierding; Bake, Muhammad Ali; Zheng, Lirong; Wang, Jiaou; Qian, Haijie; Wu, Rui; Ibrahim, Kurash

2017-08-01

The un-doped and gallium (Ga) doped multiferroic bismuth ferrite (BiFeO3) compounds were successfully synthesized by the hydrothermal technique. This is then followed by a series of detailed investigations into the influence of Ga doping on the structural, morphological, optical and magnetic properties of BiFe1 - xGaxO3 (0 ≤ x ≤ 0.15). X-ray diffraction (XRD) analyses reveal that B-site doping of Ga may lead to the transformation of its crystal structure from a rhombohedral with a space group of R3c to an orthorhombic with a space group of Pbnm phase. The scanning electron microscope (SEM) images show that doping with Ga causes a significant reduction in particle size, when compared to un-doped BiFeO3. X-ray absorption near-edge structure (XANES) spectra have also shown that as the substitution of Ga increases, the Fe K and Bi LIII-edge absorption spectra shift towards higher energy site. It also implies that doping of Ga affects the local structures of both Bi and Fe atoms. Distinct transmission band fluctuations, as shown by Fourier transform infrared (FT-IR) spectra, can provide significant evidence for a transformation in crystal structure, following the increase of Ga concentration. The magnetization hysteresis measurements show that the magnetization decreases when Ga content is x ≥ 0.05. Such a phenomenon mainly stems from the substitution of Fe for an excessive amount of Ga, resulting in reduction of both valence fluctuations and the magnetization in the BiFe1 - xGaxO3 system.

Zn-VI quasiparticle gaps and optical spectra from many-body calculations.

PubMed

Riefer, A; Weber, N; Mund, J; Yakovlev, D R; Bayer, M; Schindlmayr, Arno; Meier, C; Schmidt, W G

2017-06-01

The electronic band structures of hexagonal ZnO and cubic ZnS, ZnSe, and ZnTe compounds are determined within hybrid-density-functional theory and quasiparticle calculations. It is found that the band-edge energies calculated on the [Formula: see text] (Zn chalcogenides) or GW (ZnO) level of theory agree well with experiment, while fully self-consistent QSGW calculations are required for the correct description of the Zn 3d bands. The quasiparticle band structures are used to calculate the linear response and second-harmonic-generation (SHG) spectra of the Zn-VI compounds. Excitonic effects in the optical absorption are accounted for within the Bethe-Salpeter approach. The calculated spectra are discussed in the context of previous experimental data and present SHG measurements for ZnO.

Plasma Reflection in Multigrain Layers of Narrow-Bandgap Semiconductors

NASA Astrophysics Data System (ADS)

Zhukov, N. D.; Shishkin, M. I.; Rokakh, A. G.

2018-04-01

Qualitatively similar spectral characteristics of plasma-resonance reflection in the region of 15-25 μm were obtained for layers of electrodeposited submicron particles of InSb, InAs, and GaAs and plates of these semiconductors ground with M1-grade diamond powder. The most narrow-bandgap semiconductor InSb (intrinsic absorption edge ˜7 μm) is characterized by an absorption band at 2.1-2.3 μm, which is interpreted in terms of the model of optical excitation of electrons coupled by the Coulomb interaction. The spectra of a multigrain layer of chemically deposited PbS nanoparticles (50-70 nm) exhibited absorption maxima at 7, 10, and 17 μm, which can be explained by electron transitions obeying the energy-quantization rules for quantum dots.

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

NASA Astrophysics Data System (ADS)

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

2002-03-01

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

Resonant magnetic scattering of polarized soft x rays

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

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

1997-04-01

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

Solvation structure of the halides from x-ray absorption spectroscopy

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

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

2016-07-28

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

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

PubMed

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

2015-09-01

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

Tuning the competition between ferromagnetism and antiferromagnetism in a half-doped manganite through magnetoelectric coupling.

PubMed

Yi, Di; Liu, Jian; Okamoto, Satoshi; Jagannatha, Suresha; Chen, Yi-Chun; Yu, Pu; Chu, Ying-Hao; Arenholz, Elke; Ramesh, R

2013-09-20

We investigate the possibility of controlling the magnetic phase transition of the heterointerface between a half-doped manganite La(0.5)Ca(0.5)MnO(3) and a multiferroic BiFeO(3) (BFO) through magnetoelectric coupling. Using macroscopic magnetometry and element-selective x-ray magnetic circular dichroism at the Mn and Fe L edges, we discover that the ferroelectric polarization of BFO controls simultaneously the magnetization of BFO and La(0.5)Ca(0.5)MnO(3) (LCMO). X-ray absorption spectra at the oxygen K edge and linear dichroism at the Mn L edge suggest that the interfacial coupling is mainly derived from the superexchange between Mn and Fe t(2g) spins. The combination of x-ray absorption spectroscopy and mean-field theory calculations reveals that the d-electron modulation of Mn cations changes the magnetic coupling in LCMO, which controls the enhanced canted moments of interfacial BFO via the interfacial coupling. Our results demonstrate that the competition between ferromagnetic and antiferromagnetic instability can be modulated by an electric field at the heterointerface, providing another pathway for the electrical field control of magnetism.

The Einstein objective grating spectrometer survey of galactic binary X-ray sources

NASA Technical Reports Server (NTRS)

Vrtilek, S. D.; Mcclintock, J. E.; Seward, F. D.; Kahn, S. M.; Wargelin, B. J.

1991-01-01

The results of observations of 22 bright Galactic X-ray point sources are presented, and the most reliable measurements to date of X-ray column densities to these sources are derived. The results are consistent with the idea that some of the objects have a component of column density intrinsic to the source in addition to an interstellar component. The K-edge absorption due to oxygen is clearly detected in 10 of the sources and the Fe L and Ne K edges are detected in a few. The spectra probably reflect emission originating in a collisionally excited region combined with emission from a photoionized region excited directly by the central source.

Broadband interference lithography at extreme ultraviolet and soft x-ray wavelengths.

PubMed

Mojarad, Nassir; Fan, Daniel; Gobrecht, Jens; Ekinci, Yasin

2014-04-15

Manufacturing efficient and broadband optics is of high technological importance for various applications in all wavelength regimes. Particularly in the extreme ultraviolet and soft x-ray spectra, this becomes challenging due to the involved atomic absorption edges that rapidly change the optical constants in these ranges. Here we demonstrate a new interference lithography grating mask that can be used for nanopatterning in this spectral range. We demonstrate photolithography with cutting-edge resolution at 6.5 and 13.5 nm wavelengths, relevant to the semiconductor industry, as well as using 2.5 and 4.5 nm wavelength for patterning thick photoresists and fabricating high-aspect-ratio metal nanostructures for plasmonics and sensing applications.

Structural, electronic and photocatalytic properties of atomic defective BiI3 monolayers

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

NASA Astrophysics Data System (ADS)

Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

2013-04-01

Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, γ-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

Micro-orientation control of silicon polymer thin films on graphite surfaces modified by heteroatom doping

NASA Astrophysics Data System (ADS)

Shimoyama, Iwao; Baba, Yuji; Hirao, Norie

2017-05-01

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is applied to study orientation structures of polydimethylsilane (PDMS) films deposited on heteroatom-doped graphite substrates prepared by ion beam doping. The Si K-edge NEXAFS spectra of PDMS show opposite trends of polarization dependence for non irradiated and N2+-irradiated substrates, and show no polarization dependence for an Ar+-irradiated substrate. Based on a theoretical interpretation of the NEXAFS spectra via first-principles calculations, we clarify that PDMS films have lying, standing, and random orientations on the non irradiated, N2+-irradiated, and Ar+-irradiated substrates, respectively. Furthermore, photoemission electron microscopy indicates that the orientation of a PDMS film can be controlled with microstructures on the order of μm by separating irradiated and non irradiated areas on the graphite surface. These results suggest that surface modification of graphite using ion beam doping is useful for micro-orientation control of organic thin films.

Electronic structure and x-ray magnetic circular dichroism in Mn-doped topological insulators Bi2Se3 and Bi2Te3

NASA Astrophysics Data System (ADS)

Antonov, V. N.; Bekenov, L. V.; Uba, S.; Ernst, A.

2017-12-01

We studied the structural, electronic, and magnetic properties of Mn-doped topological insulators Bi2Se3 and Bi2Te3 within the density-functional theory (DFT) using the generalized gradient approximation (GGA) in the framework of the fully relativistic spin-polarized Dirac linear muffin-tin orbital band-structure method. The x-ray absorption spectra (XAS) and x-ray magnetic circular dichroism at the Mn K and L2 ,3 edges were investigated theoretically from first principles. The calculated results are in good agreement with experimental data. The complex fine structure of the Mn L2 ,3 XAS in Mn-doped Bi2Se3 and Bi2Te3 was found to be not compatible with a pure Mn3 + valency state. Its interpretation demands mixed valent states. The theoretically calculated x-ray emission spectra at the Mn K and L2 ,3 edges are also presented and analyzed.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

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

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

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

PubMed

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

2015-05-04

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

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

DOE PAGES

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

2015-03-18

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

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Are Hyperion and Phoebe Linked to Iapetus?

NASA Technical Reports Server (NTRS)

Jarvis, Kandy S.; Vilas, Faith; Larson, Stephen M.; Gaffey, Michael J.

1999-01-01

Narrowband reflectance spectra of the Saturnian satellites S VII Hyperion and S IX Phoebe were obtained across the 0.4 - 0.8 micron spectral region. The spectrum of Phoebe is similar to the spectrum of a C-class asteroid, with an absorption feature centered near 0.43 micron superimposed on the UV/blue intervalence charge transfer transition present in the spectrum. The spectrum of Hyperion shows the strong spectral slope apparent in spectra of many outer Solar System materials and attributed to organics. We use a linear mixing model to separate the reflectance spectrum of the dark material on Hyperion from the icy material. A distinct absorption feature centered at 0.67 micron is present. A slight inflection near 0.4 - 0.6 micron and change in slope near 0.73 micron suggesting the lower wavelength edge of an absorption are also present. These absorptions are very similar to those identified in the spectrum of the dark material on the surface of Iapetus, suggesting that the dark material on these two satellites is compositionally similar and has a similar origin. These absorption features are attributed to the (6)A(sub 1) yields (4)T(sub 2)(G) and (6)A(sub 1) yields (4)T(sub 1)(G) ferric charge transfer transitions in iron alteration minerals such as goethite and hematite that are products of the aqueous alteration of anhydrous silicates.

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.

Free-Free Absorption on Parsec Scales in Seyfert Galaxies

NASA Astrophysics Data System (ADS)

Roy, A. L.; Ulvestad, J. S.; Wilson, A. S.; Colbert, E. J. M.; Mundell, C. G.; Wrobel, J. M.; Norris, R. P.; Falcke, H.; Krichbaum, T.

Seyfert galaxies come in two main types (types 1 and 2) and the difference is probably due to obscuration of the nucleus by a torus of dense molecular material. The inner edge of the torus is expected to be ionized by optical and ultraviolet emission from the active nucleus, and will radiate direct thermal emission (e.g. NGC 1068) and will cause free-free absorption of nuclear radio components viewed through the torus (e.g. Mrk 231, Mrk 348, NGC 2639). However, the nuclear radio sources in Seyfert galaxies are weak compared to radio galaxies and quasars, demanding high sensitivity to study these effects. We have been making sensitive phase referenced VLBI observations at wavelengths between 21 and 2 cm where the free-free turnover is expected, looking for parsec-scale absorption and emission. We find that free-free absorption is common (e.g. in Mrk 348, Mrk 231, NGC 2639, NGC 1068) although compact jets are still visible, and the inferred density of the absorber agrees with the absorption columns inferred from X-ray spectra (Mrk 231, Mrk 348, NGC 2639). We find one-sided parsec-scale jets in Mrk 348 and Mrk 231, and we measure low jet speeds (typically £ 0.1 c). The one-sidedness probably is not due to Doppler boosting, but rather is probably free-free absorption. Plasma density required to produce the absorption is Ne 3 2 105 cm-3 assuming a path length of 0.1 pc, typical of that expected at the inner edge of the obscuring torus.

Palagonitic Mars: A Basalt Centric View of Surface Composition and Aqueous Alteration

NASA Technical Reports Server (NTRS)

Morris, R. V.; Graff, T. G.; Ming, D. W.; Bell, J. F., III; Le, L.; Mertzman, S. A.; Christensen, P. R.

2004-01-01

Palagonitic tephra from certain areas on Mauna Kea Volcano (Hawaii) are well-established spectral and magnetic analogues of high-albedo regions on Mars. By definition, palagonite is "a yellow or orange isotropic mineraloid formed by hydration and devitrification of basaltic glass." The yellow to orange pigment is nanometer-sized ferric oxide particles (np-Ox) dispersed throughout the hydrated basaltic glass matrix. The hydration state of the np-Ox particles and the matrix is not known, but the best Martian spectral analogues contain allophane-like materials and not crystalline phyllosilicates. Martian low-albedo regions are also characterized by a palagonite-like ferric absorption edge, but, unlike the highalbedo regions, they also show evidence for absorption by ferrous iron. Thermal emission spectra (TES) obtained by the Mars Global Surveyor Thermal Emission Spectrometer suggest that basaltic (surface Type 1) and andesitic (surface Type 2) volcanic compositions preferentially occur in southern (Syrtis Major) and northern (Acidalia) hemispheres, respectively. The absence of a ferric-bearing component in the modeling of TES spectra is in apparent conflict with VNIR spectra of Martian dark regions, as discussed above. However, the andesitic spectra have also been interpreted as oxidized basalt using phyllosilicates instead of high-SiO2 glass as endmembers in the spectral deconvolution of surface Type 2 TES spectra. We show here that laboratory VNIR and TES spectra of rinds on basaltic rocks are spectral endmembers that provide a consistent explanation for both VNIR and TES data of Martian dark regions.

UV Spectroscopy of Star-Grazing Comets Within the 49 Ceti Debris Disk

NASA Technical Reports Server (NTRS)

Miles, Brittany E.; Roberge, Aki; Welsh, Barry

2016-01-01

We present the analysis of time-variable Doppler-shifted absorption features in far-UV spectra of the unusual 49 Ceti debris disk. This nearly edge-on disk is one of the brightest known and is one of the very few containing detectable amounts of circumstellar (CS) gas as well as dust. In our two visits of Hubble Space Telescope STIS spectra, variable absorption features are seen on the wings of lines arising from CII and CIV but not for any of the other CS absorption lines. Similar variable features have long been seen in spectra of the well-studied Beta Pictoris debris disk and attributed to the transits of star-grazing comets. We calculated the velocity ranges and apparent column densities of the 49 Cet variable gas, which appears to have been moving at velocities of tens to hundreds of kms(-1) relative to the central star. The velocities in the redshifted variable event seen in the second visit show that the maximum distances of the in falling gas at the time of transit were about 0.050.2 au from the central star. A preliminary attempt at a composition analysis of the redshifted event suggests that the C/O ratio in the in falling gas is super-solar, as it is in the bulk of the stable disk gas.

Similarities in STXM-NEXAFS Spectra of Atmospheric Particles and Secondary Organic Aerosol Generated from Glyoxal, α-Pinene, Isoprene, 1,2,4-Trimethylbenzene, and d-Limonene

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

Shakya, Kabindra M.; Liu, Shang; Takahama, Satoshi

2013-02-06

Functional group composition of particles produced in smog chambers are examined using scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in order to identify characteristic spectral signatures for secondary organic aerosol (SOA). Glyoxal uptake studies showed absorption for mainly alkyl, carbon-nitrogen (C-N), and carboxylic carbonyl groups. The SOA formed from the photooxidation of α-pinene (with and without isoprene) showed stronger absorptions for alkyl and carbonyl groups than the glyoxal studies. The mass ratio of carbonyl to acid group was larger in α-pinene-only experiments relative to the mixed α-pinene-isoprene experiments. The chamber particle spectra were comparedmore » with the ambient particle spectra from multiple field campaigns to understand the potential SOA sources. One hundred nineteen particles from six field campaigns had spectral features that were considered similar to the chamber-SOA particles: MILAGRO-2006 (9 particles), VOCALS-2008 (42 particles), Whistler-2008 (22 particles), Scripps Pier-2009 (9 particles), Bakersfield-2010 (25 particles), and Whistler-2010 (12 particles). These similarities with SOA formed from glyoxal, α-pinene (with and without isoprene), 1,2,4-trimethylbenzene, and limonene provide spectroscopic evidence of SOA products from these precursors in ambient particles.« less

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

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.

Role of Ce 4 + in the scintillation mechanism of codoped Gd 3 Ga 3 Al 2 O 12 : Ce

DOE PAGES

Wu, Yuntao; Meng, Fang; Li, Qi; ...

2014-10-17

To control the time-response performance of widely used cerium-activated scintillators in cutting-edge medical-imaging devices, such as time-of-flight positron-emission tomography, a comprehensive understanding of the role of Ce valence states, especially stable Ce 4+, in the scintillation mechanism is essential. However, despite some progress made recently, an understanding of the physical processes involving Ce 4+ is still lacking. The aim of this work is to clarify the role of Ce 4+ in scintillators by studying Ca 2+ codoped Gd 3Ga 3Al 2O1 2∶Ce (GGAG∶Ce). By using a combination of optical absorption spectra and x-ray absorption near-edge spectroscopies, the correlation between Ca 2+codopingmore » content and the Ce 4+ fraction is seen. The energy-level diagrams of Ce 3+ and Ce 4+ in the Gd 3Ga 3Al 2O 12 host are established by using theoretical and experimental methods, which indicate a higher position of the 5d 1 state of Ce 4+ in the forbidden gap in comparison to that of Ce 3+. Underlying reasons for the decay-time acceleration resulting from Ca 2+ codoping are revealed, and the physical processes of the Ce 4+-emission model are proposed and further demonstrated by temperature-dependent radioluminescence spectra under x-ray excitation.« less

Role of Ce4+ in the Scintillation Mechanism of Codoped Gd3Ga3Al2O12∶Ce

NASA Astrophysics Data System (ADS)

Wu, Yuntao; Meng, Fang; Li, Qi; Koschan, Merry; Melcher, Charles L.

2014-10-01

To control the time-response performance of widely used cerium-activated scintillators in cutting-edge medical-imaging devices, such as time-of-flight positron-emission tomography, a comprehensive understanding of the role of Ce valence states, especially stable Ce44, in the scintillation mechanism is essential. However, despite some progress made recently, an understanding of the physical processes involving Ce4+ is still lacking. The aim of this work is to clarify the role of Ce4+ in scintillators by studying Ca2+ codoped Gd3Ga3Al2O12∶Ce (GGAG ∶Ce). By using a combination of optical absorption spectra and x-ray absorption near-edge spectroscopies, the correlation between Ca2+ codoping content and the Ce4+ fraction is seen. The energy-level diagrams of Ce3+ and Ce4+ in the Gd3Ga3Al2O12 host are established by using theoretical and experimental methods, which indicate a higher position of the 5d1 state of Ce4+ in the forbidden gap in comparison to that of Ce3+. Underlying reasons for the decay-time acceleration resulting from Ca2+ codoping are revealed, and the physical processes of the Ce4+-emission model are proposed and further demonstrated by temperature-dependent radioluminescence spectra under x-ray excitation.

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.

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

PubMed Central

2016-01-01

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

Surface-modified TiO2 powders with phenol derivatives: A comparative DFT and experimental study

NASA Astrophysics Data System (ADS)

Sredojević, Dušan N.; Kovač, Tijana; Džunuzović, Enis; Ðorđević, Vesna; Grgur, Branimir N.; Nedeljković, Jovan M.

2017-10-01

The charge transfer complex formation between TiO2 powder and variety of phenol derivatives (phenol, 4-nitrophenol, 4-bromophenol, 4-tert-butylphenol, hydroquinone) was achieved. The red-shift of optical absorption was observed upon surface modification of TiO2 powders with phenol derivatives. The influence of substituent functional groups in para position on the optical band gap and conduction band edge of inorganic/organic hybrids was studied using reflection spectroscopy and cyclic voltammetry. The experimental findings were supported by density functional theory calculations. The measured reflection spectra of surface-modified TiO2 powders with phenol derivatives were compared with calculated electronic excitation spectra of corresponding model systems.

Optical properties of cerium doped oxyfluoroborate glass.

PubMed

Bahadur, A; Dwivedi, Y; Rai, S B

2013-06-01

Cerium doped oxyfluoroborate glasses have been prepared and its spectroscopic properties have been discussed. It is found that the absorption edge shifts towards the lower energy side for the higher concentration of cerium dopant. Optical band gap for these glasses have been calculated and it is found that the number of non-bridging oxygen increases with cerium content. The emission spectra of these glasses have been recorded using UV laser radiations (266 and 355 nm) and it is observed that these glasses show bright blue emission. On the basis of excitation and emission spectra we have reported the existence of at least two different emission centers of Ce(3+)ions. Copyright © 2013 Elsevier B.V. All rights reserved.

N doped ZnO and ZnO nanorods based p-n homojunction fabricated by ion implantation

NASA Astrophysics Data System (ADS)

Chakraborty, Mohua; Thangavel, R.; Asokan, K.

2018-05-01

Nitrogen (N) doped and undoped Zinc Oxide (ZnO) nanorod p-n homojunctions were fabricated by ion implantation method. The structural and optical characterizations showed that the N atoms doped into the ZnO crystal lattice. The UV-Vis absorption spectra revealed shift in optical absorption edge towards higher wavelength with ion implantation on ZnO, which attributed N acceptor levels above the valence band. The current-voltage (I-V) measurements exhibit a typical semiconductor rectification characteristic indicating the electrical conductivity of the N-doped ZnO nanorod have p-type conductivity. Moreover, a high photocurrent response has been observed with these p-n homojunctions.

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

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

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

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

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

High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

DOE PAGES

Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.; ...

2016-07-01

Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO 2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO 2 is not an ionic compound as previously believed. The Th 6d occupancy in the ground statemore » was estimated to be twice that of the Th 5f states. Here, we demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.« less

Year-round measurements of ozone at 66 deg S with a visible spectrometer

NASA Technical Reports Server (NTRS)

Roscoe, Howard K.; Oldham, Derek J.; Squires, James A. C.; Pommereau, Jean-Pierre; Goutail, Florence; Sarkissian, Alain

1994-01-01

In March 1990, a zenith-sky UV-visible spectrometer of the design 'Systeme Automatique d'Obervation Zenithal' (SAOZ) was installed at Faraday in Antarctica (66.3 deg S, 64.3 deg W). SAOZ records spectra between 290 and 600 nm during daylight. Its analysis program fits laboratory spectra of constituents, at various wavelengths, to the differential of the ratio of the observed spectrum and a reference spectrum. The least-squares fitting procedure minimizes the sum-of-squares of residuals. Ozone is deduced from absorption in its visible bands between 500 and 560 nm. The fortunate colocation of this SAOZ with the well-calibrated Dobson at Faraday has allowed us to examine the calibration of the zero of the SAOZ, difficult at visible wavelengths because of the small depth of absorption. Here we describe recent improvements and limitations to this calibration, and discuss SAOZ measurements of ozone during winter in this important location at the edge of the Antarctic vortex.

Photoluminescence properties of LiF bismuth silicate glass

NASA Astrophysics Data System (ADS)

Krishnan, M. Laya; Kumar, V. V. Ravi Kanth

2018-04-01

The sample (60-X) Bi2O3-30SiO2-XLiF where X=10, 15, 25 were prepared by conventional melt quenching method. X-ray diffraction pattern conformed the amorphous nature of the prepared sample and a broad peak at 2θ=30°. The Raman spectra confirmed that the Bi can exist both network former (BiO3 pyramidal) and network modifier (BiO6 octahedral)in the glass matrix. The samples showing broad absorption at 470nm is due to the presence of Bi2+ ions, because of increasing optical basicity the absorption edge of the sample is blue shifted. The photoluminescence spectra of the glass under 350nm excitation are showing two main peaks at 430nm and 630 nm due to Bi3+ and Bi2+ respectively and 25 LBS glass showing yellow, 15LBS showing near bluish white and 10LBS showing blue luminescence. The color purity and correlated color temperature are also calculated.

Finite temperature effects on the X-ray absorption spectra of energy related materials

NASA Astrophysics Data System (ADS)

Pascal, Tod; Prendergast, David

2014-03-01

We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole (XCH) approach. Based on thermodynamic sampling via ab-initio molecular dynamics (MD) simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1 s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. This work was conducted within the Batteries for Advanced Transportation Technologies (BATT) Program, supported by the U.S. Department of Energy Vehicle Technologies Program under Contract No. DE-AC02-05CH11231.

Simulation of X-ray absorption spectra with orthogonality constrained density functional theory.

PubMed

Derricotte, Wallace D; Evangelista, Francesco A

2015-06-14

Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree-Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine.

Differences in Water Vapor Radiative Transfer among 1D Models Can Significantly Affect the Inner Edge of the Habitable Zone

NASA Astrophysics Data System (ADS)

Yang, Jun; Leconte, Jérémy; Wolf, Eric T.; Goldblatt, Colin; Feldl, Nicole; Merlis, Timothy; Wang, Yuwei; Koll, Daniel D. B.; Ding, Feng; Forget, François; Abbot, Dorian S.

2016-08-01

An accurate estimate of the inner edge of the habitable zone is critical for determining which exoplanets are potentially habitable and for designing future telescopes to observe them. Here, we explore differences in estimating the inner edge among seven one-dimensional radiative transfer models: two line-by-line codes (SMART and LBLRTM) as well as five band codes (CAM3, CAM4_Wolf, LMDG, SBDART, and AM2) that are currently being used in global climate models. We compare radiative fluxes and spectra in clear-sky conditions around G and M stars, with fixed moist adiabatic profiles for surface temperatures from 250 to 360 K. We find that divergences among the models arise mainly from large uncertainties in water vapor absorption in the window region (10 μm) and in the region between 0.2 and 1.5 μm. Differences in outgoing longwave radiation increase with surface temperature and reach 10-20 W m-2 differences in shortwave reach up to 60 W m-2, especially at the surface and in the troposphere, and are larger for an M-dwarf spectrum than a solar spectrum. Differences between the two line-by-line models are significant, although smaller than among the band models. Our results imply that the uncertainty in estimating the insolation threshold of the inner edge (the runaway greenhouse limit) due only to clear-sky radiative transfer is ≈10% of modern Earth’s solar constant (I.e., ≈34 W m-2 in global mean) among band models and ≈3% between the two line-by-line models. These comparisons show that future work is needed that focuses on improving water vapor absorption coefficients in both shortwave and longwave, as well as on increasing the resolution of stellar spectra in broadband models.

Aluminium X-ray absorption Near Edge Structure in model compounds and Earth's surface minerals

NASA Astrophysics Data System (ADS)

Ildefonse, P.; Cabaret, D.; Sainctavit, P.; Calas, G.; Flank, A.-M.; Lagarde, P.

Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of AlIV/Altotal ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by 27Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides.

DIFFERENCES IN WATER VAPOR RADIATIVE TRANSFER AMONG 1D MODELS CAN SIGNIFICANTLY AFFECT THE INNER EDGE OF THE HABITABLE ZONE

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

Yang, Jun; Wang, Yuwei; Leconte, Jérémy

An accurate estimate of the inner edge of the habitable zone is critical for determining which exoplanets are potentially habitable and for designing future telescopes to observe them. Here, we explore differences in estimating the inner edge among seven one-dimensional radiative transfer models: two line-by-line codes (SMART and LBLRTM) as well as five band codes (CAM3, CAM4-Wolf, LMDG, SBDART, and AM2) that are currently being used in global climate models. We compare radiative fluxes and spectra in clear-sky conditions around G and M stars, with fixed moist adiabatic profiles for surface temperatures from 250 to 360 K. We find thatmore » divergences among the models arise mainly from large uncertainties in water vapor absorption in the window region (10 μ m) and in the region between 0.2 and 1.5 μ m. Differences in outgoing longwave radiation increase with surface temperature and reach 10–20 W m{sup 2}; differences in shortwave reach up to 60 W m{sup 2}, especially at the surface and in the troposphere, and are larger for an M-dwarf spectrum than a solar spectrum. Differences between the two line-by-line models are significant, although smaller than among the band models. Our results imply that the uncertainty in estimating the insolation threshold of the inner edge (the runaway greenhouse limit) due only to clear-sky radiative transfer is ≈10% of modern Earth’s solar constant (i.e., ≈34 W m{sup 2} in global mean) among band models and ≈3% between the two line-by-line models. These comparisons show that future work is needed that focuses on improving water vapor absorption coefficients in both shortwave and longwave, as well as on increasing the resolution of stellar spectra in broadband models.« less

Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

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

Ren, Yuan; Xing, Yaya; Ma, Guanxiong

2015-07-15

The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cumore » atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.« less

Relativistic Effects on Reflection X-ray Spectra of AGN

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

Lee, Khee-Gan; /University Coll. London; Fuerst, Steven V.

2007-01-05

We have calculated the reflection component of the X-ray spectra of active galactic nuclei (AGN) and shown that they can be significantly modified by the relativistic motion of the accretion flow and various gravitational effects of the central black hole. The absorption edges in the reflection spectra suffer severe energy shifts and smearing. The degree of distortion depends on the system parameters, and the dependence is stronger for some parameters such as the inner radius of the accretion disk and the disk viewing inclination angles. The relativistic effects are significant and are observable. Improper treatment of the reflection component ofmore » the X-ray continuum in spectral fittings will give rise to spurious line-like features, which will mimic the fluorescent emission lines and mask the relativistic signatures of the lines.« less

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

Alteration of methotrexate binding to human serum albumin induced by oxidative stress. Spectroscopic comparative study

NASA Astrophysics Data System (ADS)

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

2016-01-01

Changes of oxidative modified albumin conformation by comparison of non-modified (HSA) and modified (oHSA) human serum albumin absorption spectra, Red Edge Excitation Shift (REES) effect and fluorescence synchronous spectra were investigated. Studies of absorption spectra indicated that changes in the value of absorbance associated with spectral changes in the region from 200 to 250 nm involve structural alterations related to variations in peptide backbone conformation. Analysis of the REES effect allowed for the observation of changes caused by oxidation in the region of the hydrophobic pocket containing the tryptophanyl residue. Synchronous fluorescence spectroscopy confirmed changes of the position of the tryptophanyl and tyrosil residues fluorescent band. Effect of oxidative stress on binding of methotrexate (MTX) was investigated by spectrofluorescence, UV-VIS and 1HNMR spectroscopy. MTX caused the fluorescence quenching of non-modified (HSA) and modified (oHSA) human serum albumin molecule. The values of binding constants, Hill's coefficients and a number of binding sites in the protein molecule in the high affinity binding site were calculated for the binary MTX-HSA and MTX-oHSA systems. For these systems, qualitative analysis in the low affinity binding sites was performed with the use of the 1HNMR technique.

Interplay of Collective Excitations in Quantum Well Intersubband Resonances

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Ning, C. Z.

2003-01-01

Intersubband resonances in a semiconductor quantum well (QW) display some of the most fascinating features involving various collective excitations such as Fermi-edge singularity (FES) and intersubband plasmon (ISP). Using a density matrix approach, we treated many-body effects such as depolarization, vertex correction, and self-energy consistently for a two-subband system. We found a systematic change in resonance spectra from FES-dominated to ISP-dominated features, as QW- width or electron density is varied. Such an interplay between FES and ISP significantly changes both line shape and peak position of the absorption spectrum. In particular, we found that a cancellation of FES and ISP undresses the resonant responses and recovers the single-particle features of absorption for semiconductors with a strong nonparabolicity such as InAs, leading to a dramatic broadening of the absorption spectrum.

Physical and optical absorption studies of Fe{sup 3+} - ions doped lithium borate glasses containing certain alkaline earths

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

Bhogi, Ashok; Kumar, R. Vijaya; Kistaiah, P., E-mail: pkistaiah@yahoo.com

Iron ion doped lithium borate glasses with the composition 15RO-25Li{sub 2}O-59B{sub 2}O{sub 3}-1Fe{sub 2}O{sub 3} (where R= Ca, Sr and Ba) have been prepared by the conventional melt quenching technique and characterized to investigate the physical and optical properties using XRD, density, molar volume and UV-Visible spectroscopy. The optical absorption spectra exhibit a band at around 460 nm which is assigned to {sup 6}A{sub 1g}(S) → 4E{sub g} (G) of Fe{sup 3+} ions with distorted octahedral symmetry. From ultraviolet absorption edges, the optical band gap and Urbach energies have been evaluated. The effect of alkaline earths on these properties ismore » discussed.« less

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

2011-03-01

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

NEXAFS spectroscopy of ionic liquids: experiments versus calculations.

PubMed

Fogarty, Richard M; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt-Talbot, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Bourne, Richard A; Chamberlain, Thomas W; Vander Hoogerstraete, Tom; Thompson, Paul B J; Hunt, Patricia A; Besley, Nicholas A; Lovelock, Kevin R J

2017-11-29

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra are reported for 12 ionic liquids (ILs) encompassing a range of chemical structures for both the sulfur 1s and nitrogen 1s edges and compared with time-dependent density functional theory (TD-DFT) calculations. The energy scales for the experimental data were carefully calibrated against literature data. Gas phase calculations were performed on lone ions, ion pairs and ion pair dimers, with a wide range of ion pair conformers considered. For the first time, it is demonstrated that TD-DFT is a suitable method for simulating NEXAFS spectra of ILs, although the number of ions included in the calculations and their conformations are important considerations. For most of the ILs studied, calculations on lone ions in the gas phase were sufficient to successfully reproduce the experimental NEXAFS spectra. However, for certain ILs - for example, those containing a protic ammonium cation - calculations on ion pairs were required to obtain a good agreement with experimental spectra. Furthermore, significant conformational dependence was observed for the protic ammonium ILs, providing insight into the predominant liquid phase cation-anion interactions. Among the 12 investigated ILs, we find that four have an excited state that is delocalised across both the cation and the anion, which has implications for any process that depends on the excited state, for example, radiolysis. Considering the collective experimental and theoretical data, we recommend that ion pairs should be the minimum number of ions used for the calculation of NEXAFS spectra of ILs.

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.

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

PubMed

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

2018-05-21

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

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.

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

DOE PAGES

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

2017-12-29

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

Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

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

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

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

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

PubMed Central

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

2018-01-01

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

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

PubMed

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

2018-05-25

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

High covalence in CuSO4 and the radicalization of sulfate: an X-ray absorption and density functional study.

PubMed

Szilagyi, Robert K; Frank, Patrick; DeBeer George, Serena; Hedman, Britt; Hodgson, Keith O

2004-12-27

Sulfur K-edge X-ray absorption spectroscopy (XAS) of anhydrous CuSO(4) reveals a well-resolved preedge transition feature at 2478.8 eV that has no counterpart in the XAS spectra of anhydrous ZnSO(4) or copper sulfate pentahydrate. Similar but weaker preedge features occur in the sulfur K-edge XAS spectra of [Cu(itao)SO(4)] (2478.4 eV) and [Cu[(CH(3))(6)tren]SO(4)] (2477.7 eV). Preedge features in the XAS spectra of transition metal ligands are generally attributed to covalent delocalization of a metal d-orbital hole into a ligand-based orbital. Copper L-edge XAS of CuSO(4) revealed that 56% of the Cu(II) 3d hole is delocalized onto the sulfate ligand. Hybrid density functional calculations on the two most realistic models of the covalent delocalization pathways in CuSO(4) indicate about 50% electron delocalization onto the sulfate oxygen-based 2p orbitals; however, at most 14% of that can be found on sulfate sulfur. Both experimental and computational results indicated that the high covalence of anhydrous CuSO(4) has made sulfate more like the radical monoanion, inducing an extensive mixing and redistribution of sulfur 3p-based unoccupied orbitals to lower energy in comparison to sulfate in ZnSO(4). It is this redistribution, rather than a direct covalent interaction between Cu(II) and sulfur, that is the origin of the observed sulfur XAS preedge feature. From pseudo-Voigt fits to the CuSO(4) sulfur K-edge XAS spectrum, a ground-state 3p character of 6% was quantified for the orbital contributing to the preedge transition, in reasonable agreement with the DFT calculation. Similar XAS fits indicated 2% sulfur 3p character for the preedge transition orbitals in [Cu(itao)SO(4)] and [Cu[(CH(3))(6)tren]SO(4)]. The covalent radicalization of ligands similar to sulfate, with consequent energy redistribution of the virtual orbitals, represents a new mechanism for the induction of ligand preedge XAS features. The high covalence of the Cu sites in CuSO(4) was found to be similar to that of Cu sites in oxidized cupredoxins, including its anistropic nature, and can serve as the simplest inorganic examples of intramolecular electron-transfer processes.

Accretion and Structure in the SW Sextantis Stars

NASA Astrophysics Data System (ADS)

Hoard, Donald Wayne

1998-09-01

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

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

PubMed Central

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A.

2016-01-01

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe3O4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level. PMID:27930297

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

DOE PAGES

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; ...

2016-12-07

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathwaymore » of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. Lastly, these results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.« less

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography.

PubMed

Zhu, Xiaohui; Hitchcock, Adam P; Bazylinski, Dennis A; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A

2016-12-20

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3 O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.

Solid-phase cadmium speciation in soil using L3-edge XANES spectroscopy with partial least-squares regression.

PubMed

Siebers, Nina; Kruse, Jens; Eckhardt, Kai-Uwe; Hu, Yongfeng; Leinweber, Peter

2012-07-01

Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least-square (PLS) regression was tested for its capability to deconvolute Cd L(3)-edge X-ray absorption near-edge structure (XANES) spectra of multi-compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R(2)) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi-compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd-contaminated soil revealing Cd(3)(PO(4))(2) (36.1%), Cd(NO(3))(2)·4H(2)O (24.5%), Cd(OH)(2) (21.7%), CdCO(3) (17.1%) and CdCl(2) (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

Mg II Spectra of Late Type Stars Used to Probe the LISM

NASA Technical Reports Server (NTRS)

Beckman, J. E.; Crivellari, L.; Franco, M.; Molaro, P.; Vladilo, G.

1984-01-01

IUE spectra of Mg II h and k in late type dwarfs and giants were used to detect and measure absorption components due to the LISM. This technique gives a method of probing the awkward range from d = 3 pc to d = 80 pc from the Sun. In spite of interpretational uncertainties the HI component of the LISM can be plotted well enough to confirm it as a cloud some 20 to 30 pc in extent, peaking sharply in density towards l(II)-25 deg., moving towards the Sun from l(II)-25 deg, b(II) = + 10 deg., at 28 Km/sec. The hole towards l(II) = 150 deg is confirmed, suggesting a solar position close to the cloud's edge in this direction.

Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates.

PubMed

Preuße, Marie; Bokarev, Sergey I; Aziz, Saadullah G; Kühn, Oliver

2016-11-01

The Frenkel exciton model was adapted to describe X-ray absorption and resonant inelastic scattering spectra of polynuclear transition metal complexes by means of the restricted active space self-consistent field method. The proposed approach allows to substantially decrease the requirements on computational resources if compared to a full supermolecular quantum chemical treatment. This holds true, in particular, in cases where the dipole approximation to the electronic transition charge density can be applied. The computational protocol was applied to the calculation of X-ray spectra of the hemin complex, which forms dimers in aqueous solution. The aggregation effects were found to be comparable to the spectral alterations due to the replacement of the axial ligand by solvent molecules.

Electrical and optical properties of nitrile rubber modified by ion implantation

NASA Astrophysics Data System (ADS)

S, Najidha; Predeep, P.

2014-10-01

Implantation of N+ ion beams are performed on to a non-conjugated elastomer, acrylonirtle butadiene rubber (NBR) with energy 60 keV in the fluence range of 1014 to 1016 ions/cm2. A decrease in the resistivity of the sample by about eight orders of magnitude is observed in the implanted samples along with color changes. The ion exposed specimens were characterized by means of UV/Vis spectroscopy which shows a shift in the absorption edge value for the as deposited polymer towards higher wavelengths. The band gap is evaluated from the absorption spectra and is found to decrease with increasing fluence. This study can possibly throw light on ion induced changes in the polymer surface.

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.

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.

An Inverse Modeling Approach to Estimating Phytoplankton Pigment Concentrations from Phytoplankton Absorption Spectra

NASA Technical Reports Server (NTRS)

Moisan, John R.; Moisan, Tiffany A. H.; Linkswiler, Matthew A.

2011-01-01

Phytoplankton absorption spectra and High-Performance Liquid Chromatography (HPLC) pigment observations from the Eastern U.S. and global observations from NASA's SeaBASS archive are used in a linear inverse calculation to extract pigment-specific absorption spectra. Using these pigment-specific absorption spectra to reconstruct the phytoplankton absorption spectra results in high correlations at all visible wavelengths (r(sup 2) from 0.83 to 0.98), and linear regressions (slopes ranging from 0.8 to 1.1). Higher correlations (r(sup 2) from 0.75 to 1.00) are obtained in the visible portion of the spectra when the total phytoplankton absorption spectra are unpackaged by multiplying the entire spectra by a factor that sets the total absorption at 675 nm to that expected from absorption spectra reconstruction using measured pigment concentrations and laboratory-derived pigment-specific absorption spectra. The derived pigment-specific absorption spectra were further used with the total phytoplankton absorption spectra in a second linear inverse calculation to estimate the various phytoplankton HPLC pigments. A comparison between the estimated and measured pigment concentrations for the 18 pigment fields showed good correlations (r(sup 2) greater than 0.5) for 7 pigments and very good correlations (r(sup 2) greater than 0.7) for chlorophyll a and fucoxanthin. Higher correlations result when the analysis is carried out at more local geographic scales. The ability to estimate phytoplankton pigments using pigment-specific absorption spectra is critical for using hyperspectral inverse models to retrieve phytoplankton pigment concentrations and other Inherent Optical Properties (IOPs) from passive remote sensing observations.

Transient bleaching of small PbS colloids. Influence of surface properties

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

Nenadovic, M.T.; Comor, M.I.; Vasic, V.

1990-08-09

Small PbS colloids with a particle diameter of 40 {angstrom} were prepared in aqueous solution, and their absorption spectra exhibit several maxima. Injection of electrons into these particles was achieved by using the pulse radiolysis technique. Excess electrons trapped on the surface lead to a blue shift in the absorption edge of colloids. The appearance of this shift depends critically on the method of colloid preparation. PbS and CdS colloids prepared at pH < 6 have long-lived bleaching, which disappears after several seconds. On the other hand, absorption bleaching does not appear after the addition of hydroxide ions to colloidalmore » solutions (pH > 8). The existence of a hydroxide ion on the particle surface most likely removes surface defects on which electrons are trapped. PbS colloids prepared in the presence of 3-mercapto-1,2-propanediol have an unstructured absorption spectrum, which is due to a wide particle size distribution (10-50 {angstrom}).« less

In Situ XANES of U and Th in Silicate Liquids at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Mallmann, G.; Wykes, J.; Berry, A.; O'Neill, H. S.; Cline, C. J., II; Turner, S.; Rushmer, T. A.

2016-12-01

Although the chemical environments of elements in silicate melts at specific conditions of temperature, pressure and oxygen fugacity (fO2) are often inferred from measurements after quenching the melts to glasses, it is widely recognized that changes may occur during the quenching process, making measurements in situ at high pressure and temperature highly desirable. A case of importance in geochemistry is the speciation of uranium in silicate melts as a function of pressure. Evidence from mineral-melt partitioning and XANES (X-ray Absorption Near-Edge Structure) spectroscopy of glasses suggests that U5+ may be stable at low pressures in the Earth's crust (along with U4+ or U6+, depending on fO2) where basaltic liquids crystallize, but not in the Earth's upper mantle where peridotite partially melts to produce such liquids. To test these observations we recorded in situ transmission U and Th L3-edge XANES spectra of U and Th-doped silicate liquids at 1.6 GPa and 1350°C using the D-DIA apparatus at the X-ray Absorption Spectroscopy Beamline of the Australian Synchrotron. Data for thorium, which occurs exclusively as a tetravalent cation under terrestrial fO2 conditions, were collected as a `control' to monitor for changes in coordination. The cell assembly consisted of a boron-epoxy cube as pressure medium, alumina sleeve and cylindrical graphite heater. The starting mix, a powdered synthetic average MORB silicate glass doped with 2 wt.% of U and Th, was loaded into San Carlos olivine capsules along with solid oxygen buffers (either Re-ReO2 or Ru-RuO2) in a sandwich arrangement. The capsule was then placed inside the graphite heater and insulated with crushable MgO powder. Temperature was monitored using a type D thermocouple. U and Th L3-edge XANES spectra were recorded throughout the heating/compression cycle and then after quenching. Our preliminary assessment indicates that the U-XANES spectra recorded for the liquid in situ at high pressure and temperature and subsequently for the quenched glass are very similar, which would suggest no apparent change in uranium coordination and/or valence state on cooling/decompression.

The Swift Burst Alert Telescope Detected Seyfert 1 Galaxies: X-Ray Broadband Properties and Warm Absorbers

NASA Technical Reports Server (NTRS)

Winter, Lisa M.; Veilleux, Sylvain; McKernan, Barry; Kallman, T.

2012-01-01

We present results from an analysis of the broadband, 0.3-195 keV, X-ray spectra of 48 Seyfert 1-1.5 sources detected in the very hard X-rays with the Swift Burst Alert Telescope (BAT). This sample is selected in an all-sky survey conducted in the 14-195 keV band. Therefore, our sources are largely unbiased toward both obscuration and host galaxy properties. Our detailed and uniform model fits to Suzaku/BAT and XMM-Newton/BAT spectra include the neutral absorption, direct power-law, reflected emission, soft excess, warm absorption, and narrow Fe I K[alpha] emission properties for the entire sample. We significantly detect O VII and O VIII edges in 52% of our sample. The strength of these detections is strongly correlated with the neutral column density measured in the spectrum. Among the strongest detections, X-ray grating and UV observations, where available, indicate outflowing material. The ionized column densities of sources with O VII and O VIII detections are clustered in a narrow range with Nwarm [approx] 1021 cm-2, while sources without strong detections have column densities of ionized gas an order of magnitude lower. Therefore, we note that sources without strong detections likely have warm ionized outflows present but at low column densities that are not easily probed with current X-ray observations. Sources with strong complex absorption have a strong soft excess, which may or may not be due to difficulties in modeling the complex spectra of these sources. Still, the detection of a flat [Gamma] [approx] 1 and a strong soft excess may allow us to infer the presence of strong absorption in low signal-to-noise active galactic nucleus spectra. Additionally, we include a useful correction from the Swift BAT luminosity to bolometric luminosity, based on a comparison of our spectral fitting results with published spectral energy distribution fits from 33 of our sources.

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

PubMed

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

2006-05-01

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

Morphological and Optical Characteristics of Chitosan(1-x):Cuox (4 ≤ x ≤ 12) Based Polymer Nano-Composites: Optical Dielectric Loss as an Alternative Method for Tauc's Model.

PubMed

Aziz, Shujahadeen B

2017-12-13

In this work, copper (Cu) nanoparticles with observable surface plasmonic resonance (SPR) peaks were synthesized by an in-situ method. Chitosan host polymer was used as a reduction medium and a capping agent for the Cu nanoparticles. The surface morphology of the samples was investigated through the use of scanning electron micrograph (SEM) technique. Copper nanoparticles appeared as chains and white specks in the SEM images. The strong peaks due to the Cu element observed in the spectrum of energy dispersive analysis of X-rays. For the nanocomposite samples, obvious peaks due to the SPR phenomena were obtained in the Ultraviolet-visible (UV-vis) spectra. The effect of Cu nanoparticles on the host band gap was understood from absorption edges shifting of absorption edges to lower photon energy. The optical dielectric loss parameter obtained from the measurable quantities was used as an alternative method to study the band structure of the samples. Quantum mechanical models drawbacks, in the study of band gap, were explained based on the optical dielectric loss. A clear dispersion region was able to be observed in refractive indices spectra of the composite samples. A linear relationship with a regression value of 0.99 was achieved between the refractive index and volume fractions of CuI content. Cu nanoparticles with various sizes and homogenous dispersions were also determined from transmission electron microscope (TEM) images.

Morphological and Optical Characteristics of Chitosan(1−x):Cuox (4 ≤ x ≤ 12) Based Polymer Nano-Composites: Optical Dielectric Loss as an Alternative Method for Tauc’s Model

PubMed Central

2017-01-01

In this work, copper (Cu) nanoparticles with observable surface plasmonic resonance (SPR) peaks were synthesized by an in-situ method. Chitosan host polymer was used as a reduction medium and a capping agent for the Cu nanoparticles. The surface morphology of the samples was investigated through the use of scanning electron micrograph (SEM) technique. Copper nanoparticles appeared as chains and white specks in the SEM images. The strong peaks due to the Cu element observed in the spectrum of energy dispersive analysis of X-rays. For the nanocomposite samples, obvious peaks due to the SPR phenomena were obtained in the Ultraviolet-visible (UV-vis) spectra. The effect of Cu nanoparticles on the host band gap was understood from absorption edges shifting of absorption edges to lower photon energy. The optical dielectric loss parameter obtained from the measurable quantities was used as an alternative method to study the band structure of the samples. Quantum mechanical models drawbacks, in the study of band gap, were explained based on the optical dielectric loss. A clear dispersion region was able to be observed in refractive indices spectra of the composite samples. A linear relationship with a regression value of 0.99 was achieved between the refractive index and volume fractions of CuI content. Cu nanoparticles with various sizes and homogenous dispersions were also determined from transmission electron microscope (TEM) images. PMID:29236074

X-ray edge spectra — a sea-boson perspective

NASA Astrophysics Data System (ADS)

Setlur, Girish S.; Meera, V.

2007-07-01

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

Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

DOE PAGES

Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; ...

2015-01-14

Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μ L = 2.8(1)μ B/Pu] and spin moments [μ S = –2.0(1)μ B/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of L z and S z are inmore » excellent agreement with the values that have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.« less

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

PubMed

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

2012-02-02

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

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.

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.

Determination of the optical absorption spectra of thin layers from their photoacoustic spectra

NASA Astrophysics Data System (ADS)

Bychto, Leszek; Maliński, Mirosław; Patryn, Aleksy; Tivanov, Mikhail; Gremenok, Valery

2018-05-01

This paper presents a new method for computations of the optical absorption coefficient spectra from the normalized photoacoustic amplitude spectra of thin semiconductor samples deposited on the optically transparent and thermally thick substrates. This method was tested on CuIn(Te0.7Se0.3)2 thin films. From the normalized photoacoustic amplitude spectra, the optical absorption coefficient spectra were computed with the new formula as also with the numerical iterative method. From these spectra, the value of the energy gap of the thin film material and the type of the optical transitions were determined. From the experimental optical transmission spectra, the optical absorption coefficient spectra were computed too, and compared with the optical absorption coefficient spectra obtained from photoacoustic spectra.

Synthesis of nanocrystalline NiO/ZnO heterostructured composite powders by sol-gel auto combustion method and their characterizations

NASA Astrophysics Data System (ADS)

Tangcharoen, Thanit; Klysubun, Wantana; Kongmark, Chanapa

2018-03-01

Nanocrystalline NiO/ZnO heterostructured composite powders were prepared by the sol-gel auto combustion method, based on nickel and zinc nitrate precursors and using diethanolamine (DEA) as novel fuel. The composition of different NiO and ZnO ratios, ranging from 100/0, 95/5, 90/10, 80/20, 60/40, 50/50, 40/60, 20/80, 10/90, 5/95 to 0/100, were studied. The structural, chemical bonding, morphological, optical, and fluorescence properties including the local atomic structure of each calcined sample were systematically investigated by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence (PL) spectroscopy, and synchrotron X-ray absorption spectroscopy (XAS), respectively. For the ZnO concentration below 20%, both XRD and Raman spectroscopy results revealed only the NiO phase. This conformed to the observation of Zn K-edge and Ni K-edge X-ray absorption near edge structure (XANES). The Zn ions found in the samples of low ZnO concentration exhibited six-fold coordination with oxygen atoms rather than the four-fold coordination found in the wurtzite (WZ) structure of ZnO. In contrast, the Ni ions which are found in the samples of low NiO concentration (≤10%) are coordinated both tetrahedrally and octahedrally by four or six oxygen atoms, respectively, rather than the six-fold coordination which is usually observed for Ni ions in the rock salt (RS) form of NiO. All analytical results obtained from experimental XANES spectra were verified by the theoretical calculation of absorption spectra using the FEFF9.7 code. The UV-DRS results showed that there was an increase in the reflectance efficiency for both infrared and visible light conditions as the content of ZnO increases; meanwhile, the values for the energy gap (Eg) of all composite samples were higher than that of pure NiO and ZnO. In addition, the PL spectra revealed major blue emission bands observed at 490 nm when the excitation wavelength was 300 nm. As the ZnO phase developed, a variety of violet emission bands occurred within the range of 400 nm-450 nm, which was obviously related to the change in Eg. The intrinsic defects occurred in the NiO/ZnO composite powders were probably responsible for this phenomenon.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

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

PubMed

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

2018-06-14

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

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.

The fastest disk wind in APM 08279+5255 and its acceleration mechanism

NASA Astrophysics Data System (ADS)

Hagino, K.; Done, C.; Odaka, H.; Watanabe, S.; Takahashi, T.

2017-10-01

The luminous high-z quasar APM 08279+5255 has the most powerful ultra-fast outflow (UFO), which is claimed as the fastest disk wind with velocity of 0.7c. This extreme velocity is very important for constraining the physical mechanism to launch the UFOs because only magnetic driving mechanism can accelerate the winds up to velocities above 0.3c, at which radiation drag effects prevent radiation driving. We reanalyze all the observed data of this source with our spectral model of highly ionized disk winds constructed by 3D Monte Carlo radiation transfer simulation. This was applied to an archetypal disk wind in PDS 456, and successfully reproduced all the spectra observed with Suzaku in spite of their strong spectral variability. By applying our spectral model to APM 08279+5255, all the spectra observed with XMM-Newton, Chandra and Suzaku are explained with less extreme outflow velocities of 0.1-0.2c. In our analysis, the high energy absorption features, which were previously interpreted as absorption lines with extremely fast velocities, are produced by iron-K absorption edges from moderately ionized clumps embedded in the highly ionized wind. We also investigate the broadband SED, and find that it is X-ray weak and UV bright, which prefers the radiation driving.

Time-dependent nonequilibrium soft x-ray response during a spin crossover

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

van Veenendaal, Michel

The rapid development of high-brilliance pulsed X-ray sources with femtosecond time resolution has created a need for a better theoretical understanding of the time-dependent soft-X-ray response of dissipative many-body quantum systems. It is demonstrated how soft-X-ray spectroscopies, such as X-ray absorption and resonant inelastic X-ray scattering at transition-metal L-edges, can provide insight into intersystem crossings, such as a spin crossover. The photoinduced doublet-to-quartet spin crossover on cobalt in Fe-Co Prussian blue analogues is used as an example to demonstrate how the X-ray response is affected by the dissipative nonequilibrium dynamics. The time-dependent soft-X-ray spectra provide a wealth of information thatmore » reflect the changes in the nonequilibrium initial state via continuously changing spectral lineshapes that cannot be decomposed into initial photoexcited and final metastable spectra, strong broadenings, a collapse of clear selection rules during the intersystem crossing, strong fluctuations in the isotropic branching ratio in X-ray absorption, and crystal-field collapse/oscillations and strongly time-dependent anti-Stokes processes in RIXS.« less

Properties of the Only Thorium Fullerene, Th@C84, Uncovered.

PubMed

Kaminský, Jakub; Vícha, Jan; Bouř, Petr; Straka, Michal

2017-04-27

Only a single thorium fullerene, Th@C 84 , has been reported to date (Akiyama, K.; et al. J. Nucl. Radiochem. Sci. 2002, 3, 151-154). Although the system was characterized by UV-vis and XANES (X-ray absorption near edge structure) spectra, its structure and properties remain unknown. In this work we used the density functional calculations to identify molecular and electronic structure of the Th@C 84 . Series of molecular structures satisfying the ThC 84 stoichiometric formula were studied comprising 24 IPR and 110 non-IPR Th@C 84 isomers as well as 9 ThC 2 @C 82 IPR isomers. The lowest energy structure is Th@C 84 -C s (10) with the singlet ground state. Its predicted electronic absorption spectra are in agreement with the experimentally observed ones. The bonding between the cage and Th was characterized as polar covalent with Th in formal oxidation state IV. The NMR chemical shifts of Th@C 84 -C s (10) were predicted to guide the future experimental efforts in identification of this compound.

Integrated experimental and theoretical approach for the structural characterization of Hg2+ aqueous solutions

NASA Astrophysics Data System (ADS)

D'Angelo, Paola; Migliorati, Valentina; Mancini, Giordano; Barone, Vincenzo; Chillemi, Giovanni

2008-02-01

The structural and dynamic properties of the solvated Hg2+ ion in aqueous solution have been investigated by a combined experimental-theoretical approach employing x-ray absorption spectroscopy and molecular dynamics (MD) simulations. This method allows one to perform a quantitative analysis of the x-ray absorption near-edge structure (XANES) spectra of ionic solutions using a proper description of the thermal and structural fluctuations. XANES spectra have been computed starting from the MD trajectory, without carrying out any minimization in the structural parameter space. The XANES experimental data are accurately reproduced by a first-shell heptacoordinated cluster only if the second hydration shell is included in the calculations. These results confirm at the same time the existence of a sevenfold first hydration shell for the Hg2+ ion in aqueous solution and the reliability of the potentials used in the MD simulations. The combination of MD and XANES is found to be very helpful to get important new insights into the quantitative estimation of structural properties of disordered systems.

Experimental and theoretical XANES of CdSxSe1-x nanostructures

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Evidence of High-Spin Ru and Universal Magnetic Anisotropy in SrRuO(3) Thin Films

DTIC Science & Technology

2012-04-17

UNIVERSAL . . . PHYSICAL REVIEW B 85, 134429 (2012) (a) (b) FIG. 5. (Color online) (a) Ru M3,2 and (b) O K - edge x-ray absorption ( XA ) and x-ray magnetic...134429-2 EVIDENCE OF HIGH-SPIN Ru AND UNIVERSAL . . . PHYSICAL REVIEW B 85, 134429 (2012) FIG. 1. (Color online) Hysteresis loops taken at 10 K of 60...SQUID magnetometry measurements. a smaller contribution from O2− ions. Typical examples of Ru and O XA spectra can be seen in Fig. 5. As there is no

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

PubMed

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

2016-06-14

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

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

The Red Edge Problem in asteroid band parameter analysis

NASA Astrophysics Data System (ADS)

Lindsay, Sean S.; Dunn, Tasha L.; Emery, Joshua P.; Bowles, Neil E.

2016-04-01

Near-infrared reflectance spectra of S-type asteroids contain two absorptions at 1 and 2 μm (band I and II) that are diagnostic of mineralogy. A parameterization of these two bands is frequently employed to determine the mineralogy of S(IV) asteroids through the use of ordinary chondrite calibration equations that link the mineralogy to band parameters. The most widely used calibration study uses a Band II terminal wavelength point (red edge) at 2.50 μm. However, due to the limitations of the NIR detectors on prominent telescopes used in asteroid research, spectral data for asteroids are typically only reliable out to 2.45 μm. We refer to this discrepancy as "The Red Edge Problem." In this report, we evaluate the associated errors for measured band area ratios (BAR = Area BII/BI) and calculated relative abundance measurements. We find that the Red Edge Problem is often not the dominant source of error for the observationally limited red edge set at 2.45 μm, but it frequently is for a red edge set at 2.40 μm. The error, however, is one sided and therefore systematic. As such, we provide equations to adjust measured BARs to values with a different red edge definition. We also provide new ol/(ol+px) calibration equations for red edges set at 2.40 and 2.45 μm.

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

NASA Technical Reports Server (NTRS)

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

The THz time domain spectra of SrB4O7 crystal

NASA Astrophysics Data System (ADS)

Wang, Yali; Hou, Bihui; Wang, Haiyan; Zhao, Guozhong; Shi, Yishi

2010-11-01

SrB4O7 (SBO) is a promising nonlinear optical crystal. It has the orthorhombic structure with group classified as Pnm2. The sample for the experiment was cut along the (001) plane and twin polishing with 1.632mm thickness. It exhibits a wider transparency range from UV to far-IR. And its absorption edge lies at 160nm. The forbidden band gap is about 7.76eV. The THz spectra of SBO crystal had been studied from 0.1 to 2.5THz. The THz time domain spectrum of SBO shows the strong resonance characters. In THz experiment, the vertical incident electromagnetic waves radiate the polished side twice along (001) orientation. The crystal turned 90 degrees relative to the first in the vertical direction. There are different optical properties in two directions. We gained the curves of the refractive index and absorption coefficient dependence of frequency in the region of 0.1-2.5THz. The absorption curves shows opposite parabola character. One is upward opening and the largest absorption coefficient is 10cm-1. The other is down opening and the less absorption coefficient is 1cm-1. The refractive index n is stable linear with frequency and it is 3 from 0.4THz to 2.5THz. But the refractive index of two directions shows the opposite tendency from 0.1 to 0.4THz. The reason of the difference is that polarized beam radiates the orthorhombic crystal. The properties of the sample show that it is possible to apply it to laser field.

X-ray diffraction and Raman investigations of thickness dependent stress effects on Pb(ZrxTi1-x)O3 thin films

NASA Astrophysics Data System (ADS)

Lappalainen, Jyrki; Lantto, Vilho; Frantti, Johannes; Hiltunen, Jussi

2006-06-01

Microstructure, film orientation, and optical transmission spectra of polycrystalline Nd-modified Pb(ZrxTi1-x)O3 films were studied as a function of film thickness. Pulsed laser deposition was used for the fabrication of films with thickness from 80to465nm on single-crystal MgO(100) substrates. Raman spectroscopy, x-ray diffraction, and spectrophotometry measurements were utilized in the film characterization. With the decreasing film thickness, films first oriented with c axis perpendicular to film surface, and then, after some critical thickness, changed to a-axis orientation. At the same time, compressive stress increased up to 1.3GPa and a clear blueshift of the optical absorption edge was found in transmission spectra.

Electrical and optical properties of nitrile rubber modified by ion implantation

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

S, Najidha; Predeep, P.

2014-10-15

Implantation of N{sup +} ion beams are performed on to a non-conjugated elastomer, acrylonirtle butadiene rubber (NBR) with energy 60 keV in the fluence range of 10{sup 14} to 10{sup 16} ions/cm{sup 2}. A decrease in the resistivity of the sample by about eight orders of magnitude is observed in the implanted samples along with color changes. The ion exposed specimens were characterized by means of UV/Vis spectroscopy which shows a shift in the absorption edge value for the as deposited polymer towards higher wavelengths. The band gap is evaluated from the absorption spectra and is found to decrease withmore » increasing fluence. This study can possibly throw light on ion induced changes in the polymer surface.« less

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

The Chemical Form of Mitochondrial Iron in Friedreich's Ataxia

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

Popescu, B.F.Gh.; Pickering, I.J.; George, G.N.

2007-07-12

Friedreich's ataxia (FRDA) results from cellular damage caused by a deficiency in the mitochondrial matrix protein frataxin. To address the effect of frataxin deficiency on mitochondrial iron chemistry, the heavy mitochondrial fraction (HMF) was isolated from primary fibroblasts from FRDA affected and unaffected individuals. X-ray absorption spectroscopy was used to characterize the chemical form of iron. Near K-edge spectra were fitted with a series of model iron compounds to determine the proportion of each iron species. Most of the iron in both affected and unaffected fibroblasts was ferrihydrite. The iron K-edge from unaffected HMFs were best fitted with poorly organizedmore » ferrihydrite modeled by frataxin whereas HMFs from affected cells were best fitted with highly organized ferrihydrite modeled by ferritin. Both had several minor iron species but these did not differ consistently with disease. Since the iron K-edge spectra of ferritin and frataxin are very similar, we present additional evidence for the presence of ferritin-bound iron in HMF. The predominant ferritin subunit in HMFs from affected cells resembled mitochondrial ferritin (MtFt) in size and antigenicity. Western blotting of native gels showed that HMF from affected cells had 3-fold more holoferritin containing stainable iron. We conclude that most of the iron in fibroblast HMF from both affected and unaffected cells is ferrihydrite but only FRDA affected cells mineralize significant iron in mitochondrial ferritin.« less

The Composition of the Iapetus Dark Material, Hyperion and Phoebe

NASA Astrophysics Data System (ADS)

Stockstill, K. R.; Larson, S. M.; Vilas, F.; Gaffey, M. J.

1996-09-01

A linear mixing model has been used to separate the high-resolution visible/near-infrared reflectance spectrum of the Iapetus dark material from spectra of the leading and trailing sides of Iapetus. A distinct absorption feature centered at 0.67 mu m is apparent in the spectrum. A slight inflection covering 0.4 to 0.6 mu m and a change in slope near 0.73 mu m suggesting the lower wavelength edge of an absorption are also present. These absorption features are attributed to (6) A1 -> (4) T2(G) and (6) A1 -> (4) T1(G) charge transfer transitions in minerals such as goethite and hematite that are products of the aqueous alteration of anhydrous silicates. We confirm the strong, positive spectral slope attributed to organic material. Broadband photometry of Phoebe using ECAS filters was acquired on four nights in 1982 (Tholen and Zellner, Icarus, 1983). On two nights covering the same side of Phoebe, the photometry tested positively for an absorption feature centered at 0.7 mu m due to oxidized iron in phyllosilicates. The opposite side of Phoebe was covered by the other two observations. The spectral difference between two opposite sides of Phoebe suggests that an impact fragmented Phoebe's parent body, producing Phoebe at the junction of two different compositional units. High resolution reflectance spectra have been obtained of the Saturnian satellites Phoebe and Hyperion, the main candidates for a circumsaturnian origin of the Iapetus dark material. These will be discussed.

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

PubMed Central

Yachandra, Vittal K

2002-01-01

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

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

PubMed

Protasenko, Vladimir; Bacinello, Daniel; Kuno, Masaru

2006-12-21

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

Retention of contaminants Cd and Hg adsorbed and intercalated in aluminosilicate clays: A first principles study

NASA Astrophysics Data System (ADS)

Crasto de Lima, F. D.; Miwa, R. H.; Miranda, Caetano R.

2017-11-01

Layered clay materials have been used to incorporate transition metal (TM) contaminants. Based on first-principles calculations, we have examined the energetic stability and the electronic properties due to the incorporation of Cd and Hg in layered clay materials, kaolinite (KAO) and pyrophyllite (PYR). The TM can be (i) adsorbed on the clay surface as well as (ii) intercalated between the clay layers. For the intercalated case, the contaminant incorporation rate can be optimized by controlling the interlayer spacing of the clay, namely, pillared clays. Our total energy results reveal that the incorporation of the TMs can be maximized through a suitable tuning of vertical distance between the clay layers. Based on the calculated TM/clay binding energies and the Langmuir absorption model, we estimate the concentrations of the TMs. Further kinetic properties have been examined by calculating the activation energies, where we found energy barriers of ˜20 and ˜130 meV for adsorbed and intercalated cases, respectively. The adsorption and intercalation of ionized TM adatoms were also considered within the deprotonated KAO surface. This also leads to an optimal interlayer distance which maximizes the TM incorporation rate. By mapping the total charge transfers at the TM/clay interface, we identify a net electronic charge transfer from the TM adatoms to the topmost clay surface layer. The effect of such a charge transfer on the electronic structure of the clay (host) has been examined through a set of X-ray absorption near edge structure (XANES) simulations, characterizing the changes of the XANES spectra upon the presence of the contaminants. Finally, for the pillared clays, we quantify the Cd and Hg K-edge energy shifts of the TMs as a function of the interlayer distance between the clay layers and the Al K-edge spectra for the pristine and pillared clays.

Tuning optical absorption and photoexcited recombination dynamics in La1-xSrxFeO3-δ through A-site substitution and oxygen vacancies

NASA Astrophysics Data System (ADS)

Smolin, Sergey; Scafetta, Mark; Choquette, Amber; Sfeir, Matthew; Baxter, Jason; May, Steven

We study optical absorption and recombination dynamics in La1-xSrxFeO3-δ thin films, uncovering the effects of tuning nominal Fe valence via A-site substitution and oxygen stoichiometry. Variable angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. These results demonstrate that while the static optical absorption is strongly dependent on Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics. Nsf: ECCS-1201957, MRI DMR-0922929, MRI DMR-1040166. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Johnson, Phillip S.

The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic structure enables the systematic design of new dyes using less expensive materials.

Determination of Cu Environments in the Cyanobacterium Anabaena flos-aquae by X-Ray Absorption Spectroscopy

PubMed Central

Kretschmer, X. C.; Meitzner, G.; Gardea-Torresdey, J. L.; Webb, R.

2004-01-01

Whole cells and peptidoglycan isolated from cell walls of the cyanobacterium Anabaena flos-aquae were lyophilized and used at pH 2 and pH 5 in Cu(II) binding studies. X-ray absorption spectra measured at the Cu K-edge were used to determine the oxidation states and chemical environments of Cu species in the whole-cell and peptidoglycan samples. In the whole-cell samples, most of the Cu retained at both pH values was coordinated by phosphate ligands. The whole-cell fractions contained significant concentrations of Cu(I) as well as Cu(II). An X-ray absorption near-edge spectrum analysis suggested that Cu(I) was coordinated by amine and thiol ligands. An analysis of the peptidoglycan fractions found that more Cu was adsorbed by the peptidoglycan fraction prepared at pH 5, due to increased chelation by amine and carboxyl ligands. The peptidoglycan fractions, also referred to as the cell wall fractions, contained little or no Cu(I). The Cu loading level was 30 times higher in the cell wall sample prepared at pH 5 than in the sample prepared at pH 2. Amine and bidentate carboxyl ligands had similar relative levels of importance in cell wall peptidoglycan samples prepared at both pH values, but phosphate coordination was insignificant. PMID:14766554

Geometry of Pt(IV) in H 2PtCl 6 aqueous solution: An X-ray absorption spectroscopic investigation

NASA Astrophysics Data System (ADS)

Chen, Xing; Chu, Wangsheng; Wang, Lei; Wu, Ziyu

2009-02-01

The noble metal ions play an important role in many chemical reactions, but at the present time they represent also potentially new environmental contaminants. There is relatively little information available to adequately assess the potential health hazards, so that to evaluate the potential hazards and identify the necessary actions to reduce the risks associated with exposure to these metals and their compounds it is important to understand the local structure around noble metal ions. In this contribution, the local coordination around platinum (IV) ions e.g., Pt 4+ in aqueous solution, has been investigated by using X-ray absorption spectroscopy (XAS). X-ray absorption near-edge spectra (XANES) of both [PtCl 6] 2- and [PtCl 4(OH) 2] 2- in an aqueous solution have been calculated using FEFF8.2 and both are characterized by an octahedral geometry. From these calculations, we may also assign a characteristic post-edge feature to a contribution of Cl d-states. From the EXAFS analysis we also determined the corresponding Pt bond distances, e.g., 2.33 Å for the Pt-Cl distance and 2.03 Å for the Pt-O distance in these aqueous solutions. The same analysis provides evidence that the peaks in the Fourier transform at about 4.0 Å are due to multiple scattering collinear Cl-Pt-Cl contributions.

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

NASA Astrophysics Data System (ADS)

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

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

Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

PubMed

Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

2016-07-20

Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model.

Suppression of spin-state transition in epitaxially strained LaCoO3

NASA Astrophysics Data System (ADS)

Pinta, C.; Fuchs, D.; Merz, M.; Wissinger, M.; Arac, E.; v. Löhneysen, H.; Samartsev, A.; Nagel, P.; Schuppler, S.

2008-11-01

Epitaxial thin films of LaCoO3 (e-LCO) exhibit ferromagnetic order with a transition temperature TC=85K while polycrystalline thin LaCoO3 films (p-LCO) remain paramagnetic. The temperature-dependent spin-state structure for both e-LCO and p-LCO was studied by x-ray absorption spectroscopy at the CoL2,3 and OK edges. Considerable spectral redistributions over temperature are observed for p-LCO . The spectra for e-LCO , on the other hand, do not show any significant changes for temperatures between 30 and 450 K at both edges, indicating that the spin state remains constant and that the epitaxial strain inhibits any population of the low-spin (S=0) state with decreasing temperature. This observation identifies an important prerequisite for ferromagnetism in e-LCO thin films.

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

PubMed

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

2015-08-19

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

Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2016-07-21

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

Copernicus ultraviolet observations of mass-loss effects in O and B stars

NASA Technical Reports Server (NTRS)

Snow, T. P., Jr.; Morton, D. C.

1976-01-01

Far-UV spectra of 47 O, B, and A stars obtained with the Copernicus satellite are examined for P Cygni profiles. For all 40 stars with displaced absorption lines, values are given for the velocities of the short-wavelength edge, the line center, and the emission peak (if present). Parts of the spectra of 42 stars are reproduced, evidence for mass motions in ground-based spectra is discussed, and the best available data are summarized on the wavelengths and oscillator strengths of most lines likely to show mass-loss effects in either visual or UV spectra. The main conclusions are that: (1) the far-UV transitions, especially resonance lines, show that mass flow is present over a much wider group of stars than revealed by visible data on subordinate lines; (2) most of the line shifts imply mass motion away from the stars; (3) mass flow occurs in all but one star brighter than a bolometric magnitude of -6.0; and (4) the observed terminal velocities generally exhibit no significant correlation with temperature, luminosity, gravity, rotational velocity, or line strength.

UV Reflectance of Jupiter's Moon Europa and Asteroid (16) Psyche

NASA Astrophysics Data System (ADS)

Becker, T. M.; Retherford, K. D.; Roth, L.; Hendrix, A.; McGrath, M. A.; Cunningham, N.; Feaga, L. M.; Saur, J.; Elkins-Tanton, L. T.; Walhund, J. E.; Molyneux, P.

2017-12-01

Surface reflectance observations of solar system objects in the UV are not only complimentary to longer wavelength observations for identifying surface composition, but can also reveal new and meaningful information about the surfaces of those bodies. On Europa, far-UV (FUV) spectral observations made by the Hubble Space Telescope (HST) show that the surface lacks a strong water ice absorption edge near 165 nm, which is intriguing because such a band has been detected on most icy satellites. This may suggest that radiolytic processing by Jupiter's magnetosphere has altered the surface, causing absorption at wavelengths longward of the H2O edge, masking this feature. Additionally, the FUV spectra are blue (increasing albedo with shorter wavelengths), and regions that are observed to be dark in the visible appear bright in the FUV. This spectral inversion, also observed on the Moon and some asteroids, may provide insight into the properties of the surface material and how they are processed.We also explore the UV reflectance spectra of the main belt asteroid (16) Psyche. This asteroid is believed to be the metallic remnant core of a differentiated asteroid, stripped of its mantle through collisions. However, there is speculation that the asteroid could have formed as-is from highly reduced metal-rich material near the Sun early in the formation of the solar system. Further, spectral observations in the infrared have revealed pyroxene and hydroxyl on the asteroid's surface, complicating the interpretation that (16) Psyche is a pure metallic object. Laboratory studies indicate that there are diagnostic spectral features in the UV that could be useful for determining the surface composition. We obtained HST observations of Psyche from 160 - 300 nm. Preliminary results show a featureless, red-sloped spectrum, inconsistent with significant amounts of pyroxene on the surface. We will present the spectra of Europa and the asteroid (16) Psyche and discuss the unique details unveiled by studies of these objects in the UV.

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Origins of extreme broadening mechanisms in near-edge x-ray spectra of nitrogen compounds

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Elam, W. T.; Denlinger, J. D.

2014-11-01

We demonstrate the observation of many-body lifetime effects in valence-band x-ray emission. A comparison of the N K α emission of crystalline ammonium nitrate to molecular-orbital calculations revealed an unexpected, extreme broadening of the NO σ recombination—so extensively as to virtually disappear. GW calculations establish that this disappearance is due to a large imaginary component of the self-energy associated with the NO σ orbitals. Building upon density-functional theory, we have calculated radiative transitions from the nitrogen 1 s level of ammonium nitrate and ammonium chloride using a Bethe-Salpeter method to include electron-hole interactions. The absorption and emission spectra of both crystals evince large, orbital-dependent sensitivity to molecular dynamics. We demonstrate that many-body effects as well as thermal and zero-point motion are vital for understanding observed spectra. A computational approach using average atomic positions and uniform broadening to account for lifetime and phonon effects is unsatisfactory.

Tetrahedral hydrocarbon nanoparticles in space: X-ray spectra

NASA Astrophysics Data System (ADS)

Bilalbegović, G.; Maksimović, A.; Valencic, L. A.

2018-06-01

It has been proposed, or confirmed, that diamond nanoparticles exist in various environments in space: close to active galactic nuclei, in the vicinity of supernovae and pulsars, in the interior of several planets in the Solar system, in carbon planets, and other exoplanets, carbon-rich stars, meteorites, in X-ray active Herbig Ae/Be stars, and in the interstellar medium. Using density functional theory methods, we calculate the carbon K-edge X-ray absorption spectrum of two large tetrahedral nanodiamonds: C26H32 and C51H52. We also study and test our methods on the astrophysical molecule CH4, the smallest C-H tetrahedral structure. A possible detection of nanodiamonds from X-ray spectra by future telescopes, such as the project Arcus, is proposed. Simulated spectra of the diffuse interstellar medium using Cyg X-2 as a source show that nanodiamonds studied in this work can be detected by Arcus, a high-resolution X-ray spectrometer mission selected by NASA for a Phase A concept study.

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

DOE PAGES

Ling, Min; Zhang, Liang; Zheng, Tianyue; ...

2017-05-10

Polysulfide shuttling has been the primary cause of failure in lithium-sulfur (Li-S) battery cycling. In this paper, we demonstrate an nucleophilic substitution reaction between polysulfides and binder functional groups can unexpectedly immobilizes the polysulfides. The substitution reaction is verified by UV–visible spectra and X-ray photoelectron spectra. The immobilization of polysulfide is in situ monitored by synchrotron based sulfur K-edge X-ray absorption spectra. The resulting electrodes exhibit initial capacity up to 20.4 mAh/cm 2, corresponding to 1199.1 mAh/g based on a micron-sulfur mass loading of 17.0 mg/cm 2. The micron size sulfur transformed into nano layer coating on the cathode bindermore » during cycling. Directly usage of nano-size sulfur promotes higher capacity of 33.7 mAh/cm 2, which is the highest areal capacity reported in Li-S battery. Finally, this enhance performance is due to the reduced shuttle effect by covalently binding of the polysulfide with the polymer binder.« less

Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery

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

Ling, Min; Zhang, Liang; Zheng, Tianyue

Polysulfide shuttling has been the primary cause of failure in lithium-sulfur (Li-S) battery cycling. In this paper, we demonstrate an nucleophilic substitution reaction between polysulfides and binder functional groups can unexpectedly immobilizes the polysulfides. The substitution reaction is verified by UV–visible spectra and X-ray photoelectron spectra. The immobilization of polysulfide is in situ monitored by synchrotron based sulfur K-edge X-ray absorption spectra. The resulting electrodes exhibit initial capacity up to 20.4 mAh/cm 2, corresponding to 1199.1 mAh/g based on a micron-sulfur mass loading of 17.0 mg/cm 2. The micron size sulfur transformed into nano layer coating on the cathode bindermore » during cycling. Directly usage of nano-size sulfur promotes higher capacity of 33.7 mAh/cm 2, which is the highest areal capacity reported in Li-S battery. Finally, this enhance performance is due to the reduced shuttle effect by covalently binding of the polysulfide with the polymer binder.« less

Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

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

Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten

2014-06-21

The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4′-dicarbo-xylato) -ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO,more » therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices.« less

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

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

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

2016-03-23

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

Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

NASA Astrophysics Data System (ADS)

Hansen, S. B.; Harding, E. C.; Knapp, P. F.; Gomez, M. R.; Nagayama, T.; Bailey, J. E.

2018-05-01

The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. We show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated by the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 1024 e/cm3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.

Modern Progress and Modern Problems in High Resolution X-ray Absorption from the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Corrales, Lia; Li, Haochuan; Heinz, Sebastian

2018-01-01

With accurate cross-sections and higher signal-to-noise, X-ray spectroscopy can directly measure Milky Way gas and dust-phase metal abundances with few underlying assumptions. The X-ray energy band is sensitive to absorption by all abundant interstellar metals — carbon, oxygen, neon, silicon, magnesium, and iron — whether they are in gas or dust form. High resolution X-ray spectra from Galactic X-ray point sources can be used to directly measure metal abundances from all phases of the interstellar medium (ISM) along singular sight lines. We show our progress for measuring the depth of photoelectric absorption edges from neutral ISM metals, using all the observations of bright Galactic X-ray binaries available in the Chandra HETG archive. The cross-sections we use take into account both the absorption and scattering effects by interstellar dust grains on the iron and silicate spectral features. However, there are many open problems for reconciling X-ray absorption spectroscopy with ISM observations in other wavelengths. We will review the state of the field, lab measurements needed, and ways in which the next generation of X-ray telescopes will contribute.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Optical Absorption Spectra of Hydrogenated Microcrystalline Silicon Films by Resonant Photothermal Bending Spectroscopy

NASA Astrophysics Data System (ADS)

Kunii, Toshie; Yoshida, Norimitsu; Hori, Yasuro; Nonomura, Shuichi

2006-05-01

A resonant photothermal bending spectroscopy (PBS) is demonstrated for the measurement of absorption coefficient spectra in hydrogenated microcrystalline silicon (μc-Si:H) and hydrogenated microcrystalline cubic silicon carbide (μc-3C-SiC:H) films. The resonant vibration technique utilized in PBS establishes the sensitivity as α d˜ 5× 10-5 in a vacuum measurement. Appling resonant PBS to μc-Si:H films, a new extra absorption coefficient αex spectrum is observed from 0.6 to 1.2 eV. The αex spectrum has a peak at ˜1.0 eV, and the localized states inducing the αex are located ˜0.35 eV below the conduction band edge of μc-Si:H. A possible explanation for the observed localized state is that an oxidation produces weak bonds at the grain boundaries and/or amorphous silicon tissues. In μc-3C-SiC:H film, an optical band-gap energy of ˜2.2 eV was demonstrated assuming an indirect optical transition. The temperature coefficient of the optical band-gap energy was ˜2.3× 10-4 eV K-1. The αex spectrum of μc-3C-SiC:H film is plateau-shaped and its magnitude is in accord with an increase in grain size.

Orbital breathing effects in the computation of x-ray d -ion spectra in solids by ab initio wave-function-based methods

DOE PAGES

Bogdanov, Nikolay A.; Bisogni, Valentina; Kraus, Roberto; ...

2016-11-21

In existing theoretical approaches to core-level excitations of transition-metal ions in solids relaxation and polarization effects due to the inner core hole are often ignored or described phenomenologically. Here, we set up an ab initio computational scheme that explicitly accounts for such physics in the calculation of x-ray absorption and resonant inelastic x-ray scattering spectra. Good agreement is found with experimental transition-metal L-edge data for the strongly correlated d 9 cuprate Li 2CuO 2, for which we also determine the absolute scattering intensities. The newly developed methodology opens the way for the investigation of even more complex d n electronicmore » structures of group VI B to VIII B correlated oxide compounds.« less

279 - Xanes Studies on UV-Irradiated Interstellar Ice Analogs: A Comparison to STARDUST Samples

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Cody, George D.; Kilcoyne, A. L. David; Nuevo, Michel; Sandford, Scott A.; Stroud, Rhonda M.; DeGregorio, Bradley T.

2010-01-01

We present C-, N-, and O-XANES (X-ray Absorption Near-Edge Spectroscopy) results of organic residues produced in the laboratory from the UV irradiation of astrophysical ice analogs containing H20, CO, CH30H, NH31 in order to mimic processes that may occur in cold icy bodies of the outer Solar System, particularly in comets, Such analyses showed that laboratory-formed organic residues mainly consist of a solid phase and an oily phase. C-XANES analysis of the solid phase suggests a rich distribution of organic functionalities, among which carbonyl groups, C=C bonds, and alcohols are present. Results from N-XANES indicate the possible presence of amide, amine, and nitrile groups, The O-XANES spectra confirmed the a-bearing groups, These results are compared with the XANES spectra obtained from STARDUST cometary samples,

Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides

NASA Astrophysics Data System (ADS)

Suganya, Krishnasamy; Kabilan, Senthamaraikannan

2004-04-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase

PubMed Central

2017-01-01

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]−/2–), to ferric and ferrous tetrathiolates ([Fe(SR)4]−/2–), to diferric and mixed-valent iron–sulfur complexes [Fe2S2R4]2–/3–. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal–iron–sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems. PMID:28653855

Angle dependence in slow photon photocatalysis using TiO2 inverse opals

NASA Astrophysics Data System (ADS)

Curti, Mariano; Zvitco, Gonzalo; Grela, María Alejandra; Mendive, Cecilia B.

2018-03-01

The slow photon effect was studied by means of the photocatalytic degradation of stearic acid over TiO2 inverse opals. The comparison of the degradation rates over inverse opals with those obtained over disordered structures at different irradiation angles showed that the irradiation at the blue edge of the stopband leads to the activation of the effect, evidenced by an improvement factor of 1.8 ± 0.6 in the reaction rate for irradiation at 40°. The rigorous coupled-wave analysis (RCWA) method was employed to confirm the source of the enhancement; simulated spectra showed an enhancement in the absorption of the TiO2 matrix that composes the inverse opal at a 40° irradiation angle, owing to an appropriate position of the stopband in relation to the absorption onset of TiO2.

Atomic gas in debris discs

NASA Astrophysics Data System (ADS)

Hales, Antonio S.; Barlow, M. J.; Crawford, I. A.; Casassus, S.

2017-04-01

We have conducted a search for optical circumstellar absorption lines in the spectra of 16 debris disc host stars. None of the stars in our sample showed signs of emission line activity in either Hα, Ca II or Na I, confirming their more evolved nature. Four stars were found to exhibit narrow absorption features near the cores of the photospheric Ca II and Na I D lines (when Na I D data were available). We analyse the characteristics of these spectral features to determine whether they are of circumstellar or interstellar origins. The strongest evidence for circumstellar gas is seen in the spectrum of HD 110058, which is known to host a debris disc observed close to edge-on. This is consistent with a recent ALMA detection of molecular gas in this debris disc, which shows many similarities to the β Pictoris system.

Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

USGS Publications Warehouse

Bassett, William A.; Anderson, Alan J.; Mayanovic, Robert A.; Chou, I.-Ming

2000-01-01

A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

Impact of magnetite nanoparticle incorporation on optical and electrical properties of nanocomposite LbL assemblies.

PubMed

Yashchenok, Alexey M; Gorin, Dmitry A; Badylevich, Mikhail; Serdobintsev, Alexey A; Bedard, Matthieu; Fedorenko, Yanina G; Khomutov, Gennady B; Grigoriev, Dmitri O; Möhwald, Helmuth

2010-09-21

Optical and electrical properties of polyelectrolyte/iron oxide nanocomposite planar films on silicon substrates were investigated for different amount of iron oxide nanoparticles incorporated in the films. The nanocomposite assemblies prepared by the layer-by-layer assembly technique were characterized by ellipsometry, atomic force microscopy, and secondary ion mass-spectrometry. Absorption spectra of the films reveal a shift of the optical absorption edge to higher energy when the number of deposited layers decreases. Capacitance-voltage and current-voltage measurements were applied to study the electrical properties of metal-oxide-semiconductor structures prepared by thermal evaporation of gold electrodes on nanocomposite films. The capacitance-voltage measurements show that the dielectric constant of the film increases with the number of deposited layers and the fixed charge and the trapped charge densities have a negative sign.

Spectroscopic characterization of novel multilayer mirrors intended for astronomical and laboratory applications

NASA Astrophysics Data System (ADS)

Ragozin, Eugene N.; Mednikov, Konstantin N.; Pertsov, Andrei A.; Pirozhkov, Alexander S.; Reva, Anton A.; Shestov, Sergei V.; Ul'yanov, Artem S.; Vishnyakov, Eugene A.

2009-05-01

We report measurements of the reflection spectra of (i) concave (spherical and parabolic) Mo/Si, Mg/Si, and Al/Zr multilayer mirrors (MMs) intended for imaging solar spectroscopy in the framework of the TESIS/CORONAS-FOTON Satellite Project and of (ii) an aperiodic Mo/Si MM optimized for maximum uniform reflectivity in the 125-250 Å range intended for laboratory applications. The reflection spectra were measured in the configuration of a transmission grating spectrometer employing the radiation of a tungsten laser-driven plasma as the source. The function of detectors was fulfilled by backside-illuminated CCDs coated with Al or Zr/Si multilayer absorption filters. High-intensity second-order interference reflection peaks at wavelengths of about 160 Å were revealed in the reflection spectra of the 304-Å Mo/Si MMs. By contrast, the second-order reflection peak in the spectra of the new-generation narrow-band (~12 Å FWHM) 304-Å Mg/Si MMs is substantially depressed. Manifestations of the NEXAFS structure of the L2, 3 absorption edges of Al and Al2O3 were observed in the spectra recorded. The broadband Mo/Si MM was employed as the focusing element of spectrometers in experiments involving (i) the charge exchange of multiply charged ions with the donor atoms of a rare-gas jet; (ii) the spectroscopic characterization of a debris-free soft X-ray radiation source excited by Nd laser pulses in a Xe jet (iii) near-IR-to-soft-X-ray frequency conversion (double Doppler effect) occurring in the retroreflection from the relativistic electron plasma wake wave (flying mirror) driven by a multiterawatt laser in a pulsed helium jet.

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

DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the FeL 2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

Advanced X-ray Spectroscopic Methods for Studying Iron-Sulfur-Containing Proteins and Model Complexes.

PubMed

DeBeer, Serena

2018-01-01

In this chapter, a brief overview of X-ray spectroscopic methods that may be utilized to obtain insight into the geometric and electronic structure of iron-sulfur proteins is provided. These methods include conventional methods, such as metal and ligand K-edge X-ray absorption, as well as more advanced methods including nonresonant and resonant X-ray emission. In each section, the basic information content of the spectra is highlighted and important experimental considerations are discussed. Throughout the chapter, recent applications to iron-sulfur-containing models and proteins are highlighted. © 2018 Elsevier Inc. All rights reserved.

LPE growth and characterization of InAs1-xNx films

NASA Astrophysics Data System (ADS)

Lv, Y. F.; Hu, S. H.; Yang, X. Y.; Wang, Y.; Sun, C. H.; Qiu, F.; Cong, R.; Dong, W. J.; Zhang, Y.; Yu, G. L.; Dai, N.

2014-07-01

A series of InAs1-xNx films have been successfully grown on (100) oriented InAs substrates by liquid phase epitaxy technique. Samples with different nitrogen contents have been analyzed by high-resolution x-ray diffraction measurement, which confirms the incorporation of N in the epilayers. N-related modes are detected in the Raman spectra of InAs1-xNx epilayers. The fundamental absorption edges of InAs1-xNx films obtained by Fourier transform infrared transmission spectroscopy exhibit a red-shift compared with that of InAs homoepilayer.

Structural motifs of pre-nucleation clusters.

PubMed

Zhang, Y; Türkmen, I R; Wassermann, B; Erko, A; Rühl, E

2013-10-07

Structural motifs of pre-nucleation clusters prepared in single, optically levitated supersaturated aqueous aerosol microparticles containing CaBr2 as a model system are reported. Cluster formation is identified by means of X-ray absorption in the Br K-edge regime. The salt concentration beyond the saturation point is varied by controlling the humidity in the ambient atmosphere surrounding the 15-30 μm microdroplets. This leads to the formation of metastable supersaturated liquid particles. Distinct spectral shifts in near-edge spectra as a function of salt concentration are observed, in which the energy position of the Br K-edge is red-shifted by up to 7.1 ± 0.4 eV if the dilute solution is compared to the solid. The K-edge positions of supersaturated solutions are found between these limits. The changes in electronic structure are rationalized in terms of the formation of pre-nucleation clusters. This assumption is verified by spectral simulations using first-principle density functional theory and molecular dynamics calculations, in which structural motifs are considered, explaining the experimental results. These consist of solvated CaBr2 moieties, rather than building blocks forming calcium bromide hexahydrates, the crystal system that is formed by drying aqueous CaBr2 solutions.

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

USGS Publications Warehouse

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Synthesis and characterization of surface-modified colloidal CdTe Quantum Dots

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

Rajh, T.; Micic, O.I.; Nozik, A.J.

1993-11-18

The controlled synthesis of quantized colloidal CdTe nanocrystals (in aqueous solutions) with narrow size distributions and stabilized against rapid oxidation was achieved by capping the quantum dot particles with 3-mercapto-1,2-propanediol. Nanocrystals (i.e., quantum dots) with mean diameters of 20, 25, 35, and 40 A were produced. Optical absorption spectra showed strong excitonic peaks at the smallest size; the absorption coefficient was shown to follow an inverse cube dependence on particle diameter, while the extinction coefficient per particle remained constant. The quantum yield for photoluminescence increased with decreasing particle size and reached 20% at 20 A. The valence band edges ofmore » the CdTe quantum dots were determined by pulse radiolysis experiments (hole injection from oxidizing radicals); the bandgaps were estimated from pulse radiolysis data (redox potentials of hole and electron injecting radicals) and from the optical spectra. The dependence of the CdTe bandgap on quantum dot size was found to be much weaker than predicted by the effective mass approximation; this result is consistent with recently published theoretical calculations by several groups. 36 refs., 5 figs., 1 tab.« less

ASCA Observation of the Dipping X-Ray Source X1916-053

NASA Technical Reports Server (NTRS)

Ko, Yuan-Kuen; Makai, Koji; Smale, Alan P.; White, Nick E.

1997-01-01

We present the results of timing and spectral studies of the dipping X-ray source X1916-053, observed by ASCA during its Performance Verification phase. The detected dipping activity is consistent with previous observations, with a period of 3008s and an intermittent secondary dip observed roughly 0.4 out of phase with the primary dip. The energy spectra of different intensity states are fitted with a power law with partial covering fraction absorption and interstellar absorption. The increase in the hardness ratio during the primary and secondary dips, and the increase in the covering fraction and column density with decreasing X-ray intensity, all imply that the dipping is caused by the photo-absorbing materials which have been suggested to be where the accreted flow hits the outer edge of the disk materials. The spectra at all intensity levels show no apparent evidence for Fe or Ne emission lines. This may be due to the low metal abundance in the accretion flow. Alternatively, the X-ray luminosity of the central source may be too weak to excite emission lines, which are assumed to be produced by X-ray photoionization of the disk materials.

Shocks in Dense Clouds in the Vela Supernova Remnant: FUSE

NASA Technical Reports Server (NTRS)

Nichols, Joy; Sonneborn, George (Technical Monitor)

2002-01-01

We have obtained 8 LWRS FUSE spectra to study a recently identified interaction of the Vela supernova remnant with a dense cloud region along its western edge. The goal is to quantify the temperature, ionization, density, and abundance characteristics associated with this shock/dense cloud interface by means of UV absorption line studies. Our detection of high-velocity absorption line C I at +90 to +130 km/s with IUE toward a narrow region interior to the Vela SNR strongly suggests the Vela supernova remnant is interacting with a dense ISM or molecular cloud. The shock/dense cloud interface is suggested by (1) the rarity of detection of high-velocity C I seen in IUE spectra, (2) its very limited spatial distribution in the remnant, and (3) a marked decrease in X-ray emission in the region immediately west of the position of these stars where one also finds a 100 micron emission ridge in IRAS images. We have investigated the shock physics and general properties of this interaction region through a focussed UV absorption line study using FUSE spectra. We have FUSE data on OVI absorption lines observed toward 8 stars behind the Vela supernova remnant (SNR). We compare the OVI observations with IUE observations of CIV absorption toward the same stars. Most of the stars, which are all B stars, have complex continua making the extraction of absorption lines difficult. Three of the stars, HD 72088, HD 72089 and HD 72350, however, are rapid rotators (v sin i less than 100 km/s) making the derivation of absorption column densities much easier. We have measured OVI and CIV column densities for the "main component" (i.e. the low velocity component) for these stars. In addition, by removing the H2 line at 1032.35A (121.6 km/s relative to OVI), we find high velocity components of OVI at approximately 150 km/s that we attribute to the shock in the Vela SNR. The column density ratios and magnitudes are compared to both steady shock models and results of hydrodynamical SNR modeling. We find that the models require the shock to be relatively slow (approximately 100 - 170 km/s) to match the FUSE data. We discuss the implications of our results for models of the evolution of the Vela SNR.

Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory

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

Fransson, Thomas; Norman, Patrick; Coriani, Sonia

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as themore » state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this method.« less

Carbon X-ray absorption spectra of fluoroethenes and acetone: a study at the coupled cluster, density functional, and static-exchange levels of theory.

PubMed

Fransson, Thomas; Coriani, Sonia; Christiansen, Ove; Norman, Patrick

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this method.

Spectromicroscopy of boron in human glioblastomas following administration of Na2B12H11SH.

PubMed

Gilbert, B; Perfetti, L; Fauchoux, O; Redondo, J; Baudat, P A; Andres, R; Neumann, M; Steen, S; Gabel, D; Mercanti, D; Ciotti, M T; Perfetti, P; Margaritondo, G; De Stasio, G

2000-07-01

Boron neutron capture therapy (BNCT) is an experimental, binary treatment for brain cancer which requires as the first step that tumor tissue is targeted with a boron-10 containing compound. Subsequent exposure to a thermal neutron flux results in destructive, short range nuclear reaction within 10 microm of the boron compound. The success of the therapy requires than the BNCT agents be well localized in tumor, rather than healthy tissue. The MEPHISTO spectromicroscope, which performs microchemical analysis by x-ray absorption near edge structure (XANES) spectroscopy from microscopic areas, has been used to study the distribution of trace quantities of boron in human brain cancer tissues surgically removed from patients first administered with the compound Na2B12H11SH (BSH). The interpretation of XANES spectra is complicated by interference from physiologically present sulfur and phosphorus, which contribute structure in the same energy range as boron. We addressed this problem with the present extensive set of spectra from S, B, and P in relevant compounds. We demonstrate that a linear combination of sulfate, phosphate and BSH XANES can be used to reproduce the spectra acquired on boron-treated human brain tumor tissues. We analyzed human glioblastoma tissue from two patients administered and one not administered with BSH. As well as weak signals attributed to BSH, x-ray absorption spectra acquired from tissue samples detected boron in a reduced chemical state with respect to boron in BSH. This chemical state was characterized by a sharp absorption peak at 188.3 eV. Complementary studies on BSH reference samples were not able to reproduce this chemical state of boron, indicating that it is not an artifact produced during sample preparation or x-ray exposure. These data demonstrate that the chemical state of BSH may be altered by in vivo metabolism.

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

Optical properties of DNA induced starch capped PbS, CdS and PbS/CdS nanocomposites

NASA Astrophysics Data System (ADS)

Das, D.; Konwar, R.; Kalita, P. K.

2015-08-01

Starch capped PbS, CdS and PbS-CdS nanocomposites are conjugated with Calf-Thymus DNA. All the materials are characterized by X-ray diffraction, high-resolution transmission electron microscopy, UV-Vis spectroscopy and photoluminescence spectroscopy. The x-ray diffraction patterns of PbS and CdS show that the materials possess polycrystalline having both cubic and hexagonal phases. High resolution transmission electron microscopic results (HRTEM) shows PbS nanoparticles of size 3 nm and that of CdS nanoparticles having average size 4 nm which exhibit tendency of agglomeration. In case of PbS/CdS, it exhibits different types of nanosheets. The UV absorption spectra of all the samples exhibit clear blue-shift with the respective bulk absorption edges. This is attributed to the strong quantum confinement in the materials. The absorption spectra also exhibit increase of the band gaps from 2.25 to 4.35 eV for PbS; 2.25-4.2 eV for CdS with decrease of molarities from 0.1 to 0.001 M as well as conjugated with DNA. The photoluminescence spectra of all PbS, CdS and PbS/CdS composites synthesized at 0.1 M molar concentration show a further blue shift and an enhancement of intensity after conjugation with DNA, but the effect is reversed i.e. occurrence of red shift and reduction of intensity for those having 0.01 M. This is due to the two competing processes of surface passivation as well as stabilization of nanocomposites governed by bio-molecules and that of Dexter energy transfer with the effective charge separation. The result shows the applicability of the materials in development of biological labels and biosensors.

Fe K Line Profile in Low-Redshift Quasars: Average Shape and Eddington Ratio Dependence

NASA Astrophysics Data System (ADS)

Inoue, Hirohiko; Terashima, Yuichi; Ho, Luis C.

2007-06-01

We analyze X-ray spectra of 43 Palomar-Green quasars observed with XMM-Newton in order to investigate their mean Fe K line profile and its dependence on physical properties. The continuum spectra of 39 objects are well reproduced by a model consisting of a power law and a blackbody modified by Galactic absorption. The spectra of the remaining four objects require an additional power-law component absorbed with a column density of ~1023 cm-2. A feature resembling an emission line at 6.4 keV, identified with an Fe K line, is detected in 33 objects. Approximately half of the sample show an absorption feature around 0.65-0.95 keV, which is due to absorption lines and edges of O VII and O VIII. We fit the entire sample simultaneously to derive average Fe line parameters by assuming a common Fe line shape. The Fe line is relatively narrow (σ=0.36 keV), with a center energy of 6.48 keV and a mean equivalent width (EW) of 248 eV. By combining black hole masses estimated from the virial method and bolometric luminosities derived from full spectral energy distributions, we examine the dependence of the Fe K line profile on the Eddington ratio. As the Eddington ratio increases, the line becomes systematically stronger (EW=130-280 eV) and broader (σ=0.1-0.7 keV), and peaks at higher energies (6.4-6.8 keV). This result suggests that the accretion rate onto the black hole directly influences the geometrical structure and ionization state of the accretion disk.

Structural, thermal and optical absorption features of heavy metal oxides doped tellurite rich glasses

NASA Astrophysics Data System (ADS)

Kaky, Kawa M.; Lakshminarayana, G.; Baki, S. O.; Kityk, I. V.; Taufiq-Yap, Y. H.; Mahdi, M. A.

In order to improve tellurite glass stability to be applicable for optical fiber amplifier applications, glasses with the composition of (70 - x)TeO2. (10)ZnO. (10)WO3. (5)Na2O. (5)TiO2. (x)Bi2O3 (x = 1, 2, 3, 4, and 5 mol%) have been produced and characterized using the related methods. Structural properties were investigated using X-ray diffraction (XRD) which confirms the non-crystalline structure and scanning electron microscopy (SEM) micrographs also confirm the XRD results. The energy dispersive X-ray (EDX) analysis profiles show that all the mentioned elements are present in the prepared glasses. Following the IR spectra, all the tellurium bonds such as stretching vibrations of TeO4 tbp and TeO3/TeO3+1 unit are revealed. Raman spectra confirm the presence of different functional groups, actually, it shows bands mainly in four spectral regions: R1 (65-150) cm-1, R2 (280-550) cm-1, R3 (880-950) cm-1 and R4 (916-926) cm-1 and the identified bands are assigned to respective molecular groups. The thermal study was carried out using Differential scanning calorimetry (DSC) which indicates good thermal stability of the synthesized glasses with increasing Bi concentration. From the optical absorption spectra, we evaluated cut-off edge wavelengths and found increasing cutoff wavelength with an increase in Bi2O3 concentration. In the UV-Visible region, optical band gap energy and allowed transitions were investigated using three methods; direct, indirect, and absorption spectrum fitting (ASF), and band gaps from indirect and ASF were matched.

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

PubMed

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

2013-08-26

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

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.

Ionic species produced on gamma radiolysis: Studies by matrix isolation technique—I. Electronic absorption spectra of perfluorosubstituted aromatic radical anions

NASA Astrophysics Data System (ADS)

Shou-te, Lian C. T.; Mittal, Jai P.

The absorption spectra of several perfluorosubstituted aromatic radical anions are compared with the corresponding perhydro compounds in which the various transitions involved have been assigned to those predicted theoretically. The electronic absorption spectra were obtained for pentafluorostyrene, pentafluorobenzaldehyde, pentafluorobenzoic acid, pentafluorobenzonitride, tetrafluorophthalic acid and pentafluoroaniline, by gamma radiolysis in 2-methyltetrahydrofuran at 77 K. A general similarity in the absorption spectra between the perfluorinated and the corresponding perhydro radical anion is observed except for a shift in the absorption band.

Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides.

PubMed

Suganya, Krishnasamy; Kabilan, Senthamaraikannan

2004-04-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed. Copyright 2003 Elsevier B.V.

Protonation state of the Cu4S2 CuZ site in nitrous oxide reductase: redox dependence and insight into reactivity

PubMed Central

Johnston, Esther M.; Dell’Acqua, Simone; Pauleta, Sofia R.; Moura, Isabel; Solomon, Edward I.

2015-01-01

Spectroscopic and computational methods have been used to determine the protonation state of the edge sulfur ligand in the Cu4S2 CuZ form of the active site of nitrous oxide reductase (N2OR) in its 3CuICuII (1-hole) and 2CuI2CuII (2-hole) redox states. The EPR, absorption, and MCD spectra of 1-hole CuZ indicate that the unpaired spin in this site is evenly delocalized over CuI, CuII, and CuIV. 1-hole CuZ is shown to have a μ2-thiolate edge ligand from the observation of S-H bending modes in the resonance Raman spectrum at 450 and 492 cm−1 that have significant deuterium isotope shifts (−137 cm−1) and are not perturbed up to pH 10. 2-hole CuZ is characterized with absorption and resonance Raman spectroscopies as having two Cu-S stretching vibrations that profile differently. DFT models of the 1-hole and 2-hole CuZ sites are correlated to these spectroscopic features to determine that 2-hole CuZ has a μ2-sulfide edge ligand at neutral pH. The slow two electron (+1 proton) reduction of N2O by 1-hole CuZ is discussed and the possibility of a reaction between 2-hole CuZ and O2 is considered. PMID:26417423

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).

Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

NASA Technical Reports Server (NTRS)

Hoepffner, Nicolas; Sathyendranath, Shubha

1993-01-01

The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

PubMed

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

Assessing the oxidation states and structural stability of the Ce analogue of brannerite

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

Aluri, Esther Rani; Bachiu, Lisa M.; Grosvenor, Andrew P.

2017-07-04

The Ce-containing analogue of brannerite (ie, UTi2O6) was previously considered to be stoichiometric (ie, CeTi2O6); however, it has recently been determined that the material is O deficient. This oxygen-deficient material has been suggested to be charged balanced by the presence of a minor concentration of Ce3+ or by the A-site being cation deficient with the Ce oxidation state being 4+. A variety of Ti-containing oxides (including brannerite) have been investigated as potential nuclear wasteforms, and it is necessary to understand the electronic structure of a proposed nuclear wasteform material as well as how the structure responds to radiation from incorporatedmore » waste elements. The radiation resistance of a material can be simulated by ion implantation. The objective of this study was to confirm the Ce oxidation state in the cation- and oxygen-deficient material (ie, Ce0.94Ti2O6 - δ) and to determine how radiation damage affects this material. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy were used to study Ce0.94Ti2O6 - δ before and after being implanted with 2 MeV Au- ions. Analysis of the Ce 3d XPS spectra from the as-synthesized samples by using a previously developed fitting method has unequivocally shown that Ce adopts both 4+ (major) and 3+ (minor) oxidation states, which was confirmed by examination of magnetic susceptibility data. Analysis of XPS and X-ray absorption near-edge spectroscopy spectra from ion-implanted materials showed that both Ce and Ti were reduced because of radiation damage and that the local coordination environments of the cations are greatly affected by radiation damage.« less

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

NASA Astrophysics Data System (ADS)

Exner, Pavel; Kuchment, Peter; Winn, Brian

2010-11-01

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

Pseudopotential calculations and photothermal lensing measurements of two-photon absorption in solids

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

White, W.T. III

1985-11-04

We have studied two-photon absorption in solids theoretically and experimentally. We have shown that it is possible to use accurate band structure techniques to compute two-photon absorption spectra within 15% of measured values in a wide band-gap material, ZnS. The empirical pseudopotential technique that we used is significantly more accurate than previous models of two-photon absorption in zinc blende materials, including present tunneling theories (which are essentially parabolic-band results in disguise) and the nonparabolic-band formalism of Pidgeon et al. and Weiler. The agreement between our predictions and previous measurements allowed us to use ZnS as a reference material in ordermore » to validate a technique for measuring two-photon absorption that was previously untried in solids, pulsed dual-beam thermal lensing. With the validated technique, we examined nonlinear absorption in one other crystal (rutile) and in several glasses, including silicates, borosilicates, and one phosphate glass. Initially, we believed that the absorption edges of all the materials were comparable; however, subsequent evidence suggested that the effective band-gap energies of the glasses were above the energy of two photons in our measurement. Therefore, we attribute the nonlinear absorption that we observed in glasses to impurities or defects. The measured nonlinear absorption coefficients were of the order of a few cm/TW in the glasses and of the order of 10 cm/GW in the crystals, four orders of magnitude higher than in glasses. 292 refs.« less

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Scanning transmission X-ray microscopy probe for in situ mechanism study of graphene-oxide-based resistive random access memory.

PubMed

Nho, Hyun Woo; Kim, Jong Yun; Wang, Jian; Shin, Hyun-Joon; Choi, Sung-Yool; Yoon, Tae Hyun

2014-01-01

Here, an in situ probe for scanning transmission X-ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K- and O K-edges, both the RRAM junctions and the I0 junction were fabricated on a single Si3N4 membrane to obtain local XANES spectra at these absorption edges with more delicate I0 normalization. Using this probe combined with the synchrotron-based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K-edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.

Quanty for core level spectroscopy - excitons, resonances and band excitations in time and frequency domain

NASA Astrophysics Data System (ADS)

Haverkort, Maurits W.

2016-05-01

Depending on the material and edge under consideration, core level spectra manifest themselves as local excitons with multiplets, edge singularities, resonances, or the local projected density of states. Both extremes, i.e., local excitons and non-interacting delocalized excitations are theoretically well under control. Describing the intermediate regime, where local many body interactions and band-formation are equally important is a challenge. Here we discuss how Quanty, a versatile quantum many body script language, can be used to calculate a variety of different core level spectroscopy types on solids and molecules, both in the frequency as well as the time domain. The flexible nature of Quanty allows one to choose different approximations for different edges and materials. For example, using a newly developed method merging ideas from density renormalization group and quantum chemistry [1-3], Quanty can calculate excitons, resonances and band-excitations in x-ray absorption, photoemission, x-ray emission, fluorescence yield, non-resonant inelastic x-ray scattering, resonant inelastic x-ray scattering and many more spectroscopy types. Quanty can be obtained from: http://www.quanty.org.

Evidence for Weakly Correlated Oxygen Holes in the Highest-Tc Cuprate Superconductor HgBa2 Ca2 Cu3 O8 +δ

NASA Astrophysics Data System (ADS)

Chainani, A.; Sicot, M.; Fagot-Revurat, Y.; Vasseur, G.; Granet, J.; Kierren, B.; Moreau, L.; Oura, M.; Yamamoto, A.; Tokura, Y.; Malterre, D.

2017-08-01

We study the electronic structure of HgBa2 Ca2 Cu3 O8 +δ (Hg1223; Tc=134 K ) using photoemission spectroscopy (PES) and x -ray absorption spectroscopy (XAS). Resonant valence band PES across the O K edge and Cu L edge identifies correlation satellites originating in O 2 p and Cu 3 d two-hole final states, respectively. Analyses using the experimental O 2 p and Cu 3 d partial density of states show quantitatively different on-site Coulomb energy for the Cu site (Ud d=6.5 ±0.5 eV ) and O site (Up p=1.0 ±0.5 eV ). Cu2 O7 -cluster calculations with nonlocal screening explain the Cu 2 p core level PES and Cu L -edge XAS spectra, confirm the Ud d and Up p values, and provide evidence for the Zhang-Rice singlet state in Hg1223. In contrast to other hole-doped cuprates and 3 d -transition metal oxides, the present results indicate weakly correlated oxygen holes in Hg1223.

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.

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

Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

PubMed

Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

2012-04-18

An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society

Fluctuations at the blue edge of saturated wind lines in IUE spectra of O-type stars

NASA Technical Reports Server (NTRS)

Owocki, Stanley P.; Fullerton, Alex

1993-01-01

We examine basic issues involved in synthesizing resonance-line profiles from 1-D, dynamical models of highly structured hot-star winds. Although these models exhibit extensive variations in density as well as velocity, the density scale length is still typically much greater than the Sobolev length. The line transfer is thus treated using a Sobolev approach, as generalized by Rybicki & Hummer (1978) to take proper account of the multiple Sobolev resonances arising from the nonmonotonic velocity field. The resulting reduced-Lambda-matrix equation describing nonlocal coupling of the source function is solved by iteration, and line profiles and then derived from formal solution integration using this source function. The more appropriate methods that instead use either a stationary or a structured, local source function yield qualitatively similar line-profiles, but are found to violate photon conservation by 10 percent or more. The full results suggest that such models may indeed be able to reproduce naturally some of the qualitative properties long noted in observed UV line profiles, such as discrete absorption components in unsaturated lines, or the blue-edge variability in saturated lines. However, these particular models do not yet produce the black absorption troughs commonly observed in saturated lines, and it seems that this and other important discrepancies (e.g., in acceleration time scale of absorption components) may require development of more complete models that include rotation and other 2-D and/or 3-D effects.

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids.

PubMed

Shanthi, M; Kabilan, S

2007-06-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids

NASA Astrophysics Data System (ADS)

Shanthi, M.; Kabilan, S.

2007-06-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Electronic and magnetic properties of epitaxial perovskite SrCrO3(001)

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

Zhang, Hongliang; Du, Yingge; Sushko, Petr

2015-06-24

We have investigated the intrinsic properties of SrCrO3 epitaxial thin films synthesized by molecular beam epitaxy. We find compelling evidence that SrCrO3 is a correlated metal. X-ray photoemission valence band and O K-edge x-ray absorption spectra indicate a strongly hybridized Cr3d-O2p state crossing the Fermi level, leading to metallic behavior. Comparison between valence band spectra near the Fermi level and the densities of states calculated using density functional theory (DFT) also suggests the presence of coherent and incoherent states and points to a strong electron-electron correlation effects. The magnetic susceptibility can be described by Pauli paramagnetism at temperatures above 100more » K, but reveals antiferromagnetic behavior at lower temperatures resulting from orbital ordering as suggested by Ortega-San-Martin et al. [Phys. Rev. Lett. 99, 255701 (2007)].« less

Microstructure and optical properties of nanocrystalline Cu2O thin films prepared by electrodeposition.

PubMed

Jiang, Xishun; Zhang, Miao; Shi, Shiwei; He, Gang; Song, Xueping; Sun, Zhaoqi

2014-01-01

Cuprous oxide (Cu2O) thin films were prepared by using electrodeposition technique at different applied potentials (-0.1, -0.3, -0.5, -0.7, and -0.9 V) and were annealed in vacuum at a temperature of 100°C for 1 h. Microstructure and optical properties of these films have been investigated by X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), UV-visible (vis) spectrophotometer, and fluorescence spectrophotometer. The morphology of these films varies obviously at different applied potentials. Analyses from these characterizations have confirmed that these films are composed of regular, well-faceted, polyhedral crystallites. UV-vis absorption spectra measurements have shown apparent shift in optical band gap from 1.69 to 2.03 eV as the applied potential becomes more cathodic. The emission of FL spectra at 603 nm may be assigned as the near band-edge emission.

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

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

Optical and electrical properties of copper-incorporated ZnS films applicable as solar cell absorbers

NASA Astrophysics Data System (ADS)

Mehrabian, M.; Esteki, Z.; Shokrvash, H.; Kavei, G.

2016-10-01

Un-doped and Cu-doped ZnS (ZnS:Cu) thin films were synthesized by Successive Ion Layer Absorption and Reaction (SILAR) method. The UV-visible absorption studies have been used to calculate the band gap values of the fabricated ZnS:Cu thin films. It was observed that by increasing the concentration of Cu2+ ions, the Fermi level moves toward the edge of the valence band of ZnS. Photoluminescence spectra of un-doped and Cu-doped ZnS thin films was recorded under 355 nm. The emission spectrum of samples has a blue emission band at 436 nm. The peak positions of the luminescence showed a red shift as the Cu2+ ion concentration was increased, which indicates that the acceptor level (of Cu2+) is getting close to the valence band of ZnS.

Spectroscopic ellipsometry study of Cu2ZnSnS4 bulk poly-crystals

NASA Astrophysics Data System (ADS)

Levcenko, S.; Hajdeu-Chicarosh, E.; Garcia-Llamas, E.; Caballero, R.; Serna, R.; Bodnar, I. V.; Victorov, I. A.; Guc, M.; Merino, J. M.; Pérez-Rodriguez, A.; Arushanov, E.; León, M.

2018-04-01

The linear optical properties of Cu2ZnSnS4 bulk poly-crystals have been investigated using spectroscopic ellipsometry in the range of 1.2-4.6 eV at room temperature. The characteristic features identified in the optical spectra are explained by using the Adachi analytical model for the interband transitions at the corresponding critical points in the Brillouin zone. The experimental data have been modeled over the entire spectral range taking into account the lowest E0 transition near the fundamental absorption edge and E1A and E1B higher energy interband transitions. In addition, the spectral dependences of the refractive index, extinction coefficient, absorption coefficient, and normal-incidence reflectivity values have been accurately determined and are provided since they are essential data for the design of Cu2ZnSnS4 based optoelectronic devices.

Structural reconstruction of the catalytic center of LiPDF through multiple scattering calculation with MXAN

NASA Astrophysics Data System (ADS)

Guo, Xiaoyun; Chu, Wangsheng; Ma, Sixuan; Gong, Weimin; Benfatto, Maurizio; Hu, Tiandou; Xie, Yaning; Wu, ZiYu

2006-11-01

Peptide deformylase (PDF, EC 3.5.1.27) is essential for the normal growth of eubacterium but not for mammalians. Recently, PDF has been studied as a target for new antibiotics. In this paper, X-ray absorption spectroscopy was employed to determine the local structure around the zinc ion of PDF from Leptospira Interrogans in dry powder, because it is very difficult to obtain the crystallized sample of LiPDF. We performed X-ray absorption near edge structure (XANES) calculation and reconstructed successfully the local geometry of the active center, and the results from calculations show that a water molecule (Wat1) has moved towards the zinc ion and lies in the distance range to coordinate with the zinc ion weakly. In addition, the sensitivity of theoretical spectra to the different ligand bodies was evaluated in terms of goodness-of-fit.

X-ray absorption spectroscopy to determine originating depth of electrons that form an inelastic background of Auger electron spectrum

NASA Astrophysics Data System (ADS)

Isomura, Noritake; Cui, Yi-Tao; Murai, Takaaki; Oji, Hiroshi; Kimoto, Yasuji

2017-07-01

In Auger electron spectroscopy (AES), the spectral background is mainly due to inelastic scattering of Auger electrons that lose their kinetic energy in a sample bulk. To investigate the spectral components within this background for SiO2(19.3 nm)/Si(100) with known layer thickness, X-ray absorption spectroscopy (XAS) was used in the partial-electron-yield (PEY) mode at several electron kinetic energies to probe the background of the Si KLL Auger peak. The Si K-edge PEY-XAS spectra constituted of both Si and SiO2 components at each kinetic energy, and their component fractions were approximately the same as those derived from the simulated AES background for the same sample structure. The contributions of Auger electrons originating from layers at different depths to the inelastic background could thus be identified experimentally.

Liquid helium cryostat with internal fluorescence detection for x-ray absorption studies in the 2-6 keV energy region

NASA Astrophysics Data System (ADS)

McFarlane Holman, Karen L.; Latimer, Matthew J.; Yachandra, Vittal K.

2004-06-01

X-ray absorption spectroscopy (XAS) in the intermediate x-ray region (2-6 keV) for dilute biological samples has been limited because of detector/flux limitations and inadequate cryogenic instrumentation. We have designed and constructed a new tailpiece/sample chamber for a commercially available liquid helium cooled cryostat which overcomes difficulties related to low fluorescence signals by using thin window materials and incorporating an internal photodiode detector. With the apparatus, XAS data at the Cl, S, and Ca K edges have been collected on frozen solutions and biological samples at temperatures down to 60 K. A separate chamber has been incorporated for collecting room-temperature spectra of standard compounds (for energy calibration purposes) which prevents contamination of the cryostat chamber and allows the sample to remain undisturbed, both important concerns for studying dilute and radiation-sensitive samples.