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Sample records for absorption spectra xas

  1. 1913–2013 – The centennial of X-ray absorption spectroscopy (XAS): Evidences about a question still open

    Energy Technology Data Exchange (ETDEWEB)

    Mottana, Annibale, E-mail: annibale.mottana@uniroma3.it [Università degli Studi Roma Tre, Dipartimento di Scienze, Largo S. Leonardo Murialdo 1, I-00146 Roma (Italy); Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, Via E. Fermi 40, I-00044 Frascati, RM (Italy)

    2014-10-15

    Highlights: • X-ray Absorption Spectroscopy (XAS) cannot be dated exactly as for its birth. • The assumed discoverer, M. de Broglie, was preceded by J. Herweg in the submission. • However, both their spectra were found to be mistaken. • Before the work of W. Stenström and H. Fricke no sure evidence of XAS is published. • The solution is, probably, taking October 1, 1918 as XAS fictitious birthday. - Abstract: In 1913 J. Herweg first (June 30) and M. de Broglie slightly later (November 17) claimed the discovery of a series of spots and lines closely following the main absorption edges of heavy metals, which they interpreted as the proof of the existence of X-ray spectra analogous to light spectra. In the following year they documented their discoveries via photographic plates. However, they were both discredited: Herweg by G.E.M. Jauncey, who showed that his spectra, taken on Pt and W, did not obey Moseley's rule; de Broglie by W.H. Bragg, M. Siegbahn and E. Wagner, who showed that his lines were in fact the fluorescence lines of the Ag and Br constituents of the photographic emulsion. Consequently, W. Stenström's description (sent to publisher on July 2, 1918) of certain photographically recorded and graphically rendered modulations near the M-series edges of heavy metals may possibly be the first published evidence of true X-ray absorption spectra. Indeed, they were interpreted as such by W. Kossel (1920) in his seminal theoretical paper. Otherwise, H. Fricke's table, although printed in 1920, which exhibits the photographic plate of sulphur absorption dated October 1, 1918, and its graphical rendering by a photometric method, is the first unequivocally dated evidence of recorded modulations at a XAS K-edge.

  2. Donor impurity-related optical absorption spectra in GaAs-Ga{sub 1-x}Al{sub x}As quantum wells: hydrostatic pressure and {gamma}-X conduction band mixing effects

    Energy Technology Data Exchange (ETDEWEB)

    Mora-Ramos, M.E. [Facultad de Ciencias, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, C.P. 62209, Cuernavaca, MOR (Mexico); Inst. de Ciencia de Materiales de Madrid, CSIC, Sor Juana Ines de la Cruz 3, 28049 Madrid (Spain); Lopez, S.Y. [Fac. de Educacion, Universidad de Antioquia, AA 1226, Medellin (Colombia); Duque, C.A. [Inst. de Fisica, Universidad de Antioquia, AA 1226, Medellin (Colombia); Velasco, V.R. [Inst. de Ciencia de Materiales de Madrid, CSIC, Sor Juana Ines de la Cruz 3, 28049 Madrid (Spain)

    2007-07-01

    Using a variational procedure within the effective mass approximation, the mixing between the {gamma} and X conduction band valleys in GaAs-Ga{sub 1-x}Al{sub x}As quantum wells is investigated by taking into account the effect of applied hydrostatic pressure. Some optical properties such as donor and/or acceptor binding energy and impurity-related transition energies are calculated and comparisons with available experimental data are presented. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Science.gov (United States)

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

    2018-03-01

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

  4. X-ray absorption spectra and emission spectra of plasmas

    International Nuclear Information System (INIS)

    Peng Yonglun; Yang Li; Wang Minsheng; Li Jiaming

    2002-01-01

    The author reports a theoretical method to calculate the resolved absorption spectra and emission spectra (optically thin) of hot dense plasmas. Due to its fully relativistic treatment incorporated with the quantum defect theory, it calculates the absorption spectra and emission spectra for single element or multi-element plasmas with little computational efforts. The calculated absorption spectra of LTE gold plasmas agree well with the experimental ones. It also calculates the optical thin emission spectra of LTE gold plasmas, which is helpful to diagnose the plasmas of relevant ICF plasmas. It can also provide the relevant parameters such as population density of various ionic stages, precise radiative properties for ICF studies

  5. Optical absorption spectra of Ag-11 isomers

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; Fernandez, E. M.

    2009-01-01

    The optical absorption spectra of the three most; stable structural isomers of the Ag-11 cluster were calculated using the time-dependent, density functional theory within the Casida formalism. The slightly different, spectra, of the isomers may permit the identification of the ground-stale confi......The optical absorption spectra of the three most; stable structural isomers of the Ag-11 cluster were calculated using the time-dependent, density functional theory within the Casida formalism. The slightly different, spectra, of the isomers may permit the identification of the ground...

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

    Science.gov (United States)

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

    2017-02-06

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

  7. Absorption spectra of AA-stacked graphite

    International Nuclear Information System (INIS)

    Chiu, C W; Lee, S H; Chen, S C; Lin, M F; Shyu, F L

    2010-01-01

    AA-stacked graphite shows strong anisotropy in geometric structures and velocity matrix elements. However, the absorption spectra are isotropic for the polarization vector on the graphene plane. The spectra exhibit one prominent plateau at middle energy and one shoulder structure at lower energy. These structures directly reflect the unique geometric and band structures and provide sufficient information for experimental fitting of the intralayer and interlayer atomic interactions. On the other hand, monolayer graphene shows a sharp absorption peak but no shoulder structure; AA-stacked bilayer graphene has two absorption peaks at middle energy and abruptly vanishes at lower energy. Furthermore, the isotropic features are expected to exist in other graphene-related systems. The calculated results and the predicted atomic interactions could be verified by optical measurements.

  8. Genesis of Co/SiO2 catalysts : XAS study at the cobalt L-III,L- II absorption edges

    NARCIS (Netherlands)

    Bazin, D.; Kovacs, I.; Guczi, L.; Parent, P.; Laffon, C.; De Groot, F.; Ducreux, O.; Lynch, J.

    2000-01-01

    Silica-supported cobalt catalysts have been investigated by soft X-ray absorption techniques. Soft X-ray absorption spectra were collected at the Co LII,III edge during in situ reduction of calcined samples in a stream of hydrogen in the temperature range between 300 and 650°C. Using reference

  9. Absorption Spectra of Gold Nanoparticle Suspensions

    Science.gov (United States)

    Anan'eva, M. V.; Nurmukhametov, D. R.; Zverev, A. S.; Nelyubina, N. V.; Zvekov, A. A.; Russakov, D. M.; Kalenskii, A. V.; Eremenko, A. N.

    2018-02-01

    Three gold nanoparticle suspensions are obtained, and mean radii in distributions - (6.1 ± 0.2), (11.9 ± 0.3), and (17.3 ± 0.7) nm - are determined by the transmission electron microscopy method. The optical absorption spectra of suspensions are obtained and studied. Calculation of spectral dependences of the absorption index of suspensions at values of the gold complex refractive index taken from the literature showed a significant deviation of experimental and calculated data in the region of 450-800 nm. Spectral dependences of the absorption of suspensions are simulated within the framework of the Mie-Drude theory taking into account the interband absorption in the form of an additional term in the imaginary part of the dielectric permittivity of the Gaussian type. It is shown that to quantify the spectral dependences in the region of the plasmon absorption band of nanoparticles, correction of the parameters of the interband absorption is necessary in addition to the increase of the relaxation parameter of the Drude theory. Spectral dependences of the dielectric permittivity of gold in nanodimensional state are refined from the solution of the inverse problem. The results of the present work are important for predicting the special features of operation of photonic devices and optical detonators based on gold nanoparticles.

  10. Molecular geometry in the ultraviolet absorption spectra

    International Nuclear Information System (INIS)

    Albuquerque, S.F. de; Monteiro, L.S.; Adamis, L.M.B.; Baltar, M.C.P.; Silva, R.M. da

    1977-01-01

    The ultraviolet absorption spectra may be sensibly affected by steric effects. These effects can cause a lot of difficulties and unexpected changes in spectrum. The most general source of such difficulties is steric inhibition of resonance. In addition to this, ultraviolet epectra may be markedly changed by steric factors which change the positions of dipoles in the molecule with respect to each other and by the interaction of nonconjugated chromophores suitably located in space. We have studied in detail each of these effects presenting a lot of usual and importants examples in Organic Chemistry. Others relevants subjects were not considerated in this present work [pt

  11. Biological X-ray absorption spectroscopy (BioXAS): a valuable tool for the study of trace elements in the life sciences.

    Science.gov (United States)

    Strange, Richard W; Feiters, Martin C

    2008-10-01

    Using X-ray absorption spectroscopy (XAS) the binding modes (type and number of ligands, distances and geometry) and oxidation states of metals and other trace elements in crystalline as well as non-crystalline samples can be revealed. The method may be applied to biological systems as a 'stand-alone' technique, but it is particularly powerful when used alongside other X-ray and spectroscopic techniques and computational approaches. In this review, we highlight how biological XAS is being used in concert with crystallography, spectroscopy and computational chemistry to study metalloproteins in crystals, and report recent applications on relatively rare trace elements utilised by living organisms and metals involved in neurodegenerative diseases.

  12. Influence of interstitial solutions (H, N) on cerium electronic state in Ce-Fe intermetallic compounds: X-ray Absorption Spectroscopy (XAS) study

    International Nuclear Information System (INIS)

    Chaboy, J.; Marcelli, A.; Bozukov, L.

    1995-03-01

    It is presented an x-ray absorption spectroscopy (XAS) investigation performed at the L-edges of the rare-earth and at the K-edge of iron in the R-Fe intermetallic compounds (La, Ce) 2 Fe 14 BH χ and Ce 2 Fe 17 (H,N) χ , to elucidate the role of the interstitial doping into the electronic and magnetic properties of these systems. Comparison with x-ray circular magnetic dichroism (XCMD) experiments has been carried out to clarify the localization of 4f magnetic moment at the Ce sites upon hydriding. Both XAS and XCMD results evidence the interplay between the structural and magnetic changes, that are associated to the modification of the hybridization between the Fe(3d) and Ce(5d) bands

  13. Photoacoustic absorption spectra of atmospheric gases near 7603 cm-1

    International Nuclear Information System (INIS)

    Lawton, S.A.; Bragg, S.L.

    1984-01-01

    Absorption spectra of carbon monoxide, water vapor, memane, and ammonia are presented as part of an effort to determine absolute absorption cross sections for some atmospheric gases at the iodine laser wavelength

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

    Science.gov (United States)

    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.

  15. Determination of the optical absorption spectra of thin layers from their photoacoustic spectra

    Science.gov (United States)

    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.

  16. Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring

    Science.gov (United States)

    2016-03-31

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9675 Absorption- Edge -Modulated Transmission Spectra for Water Contaminant...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption- Edge -Modulated Transmission Spectra for Water Contaminant Monitoring...contaminants, within a volume of sampled solution, requires sufficient sensitivity. The present study examines the sensitivity of absorption- edge

  17. Revisiting the total ion yield x-ray absorption spectra of liquid water microjets

    International Nuclear Information System (INIS)

    Saykally, Richard J; Cappa, Chris D.; Smith, Jared D.; Wilson, Kevin R.; Saykally, Richard J.

    2008-01-01

    Measurements of the total ion yield (TIY) x-ray absorption spectrum (XAS) of liquid water by Wilson et al. (2002 J. Phys.: Condens. Matter 14 L221 and 2001 J. Phys. Chem. B 105 3346) have been revisited in light of new experimental and theoretical efforts by our group. Previously, the TIY spectrum was interpreted as a distinct measure of the electronic structure of the liquid water surface. However, our new results indicate that the previously obtained spectrum may have suffered from as yet unidentified experimental artifacts. Although computational results indicate that the liquid water surface should exhibit a TIY-XAS that is fundamentally distinguishable from the bulk liquid XAS, the new experimental results suggest that the observable TIY-XAS is actually nearly identical in appearance to the total electron yield (TEY-)XAS, which is a bulk probe. This surprising similarity between the observed TIY-XAS and TEY-XAS likely results from large contributions from x-ray induced electron stimulated desorption of ions, and does not necessarily indicate that the electronic structure of the bulk liquid and liquid surface are identical

  18. Investigation of IR absorption spectra of oral cavity bacteria

    Science.gov (United States)

    Belikov, Andrei V.; Altshuler, Gregory B.; Moroz, Boris T.; Pavlovskaya, Irina V.

    1996-12-01

    The results of comparative investigation for IR and visual absorption spectra of oral cavity bacteria are represented by this paper. There are also shown the main differences in absorption spectra of such pure bacteria cultures as : E- coli, Candida, Staph, Epidermidis, and absorption spectra of bacteria colonies cultured in tooth root canals suspected to harbour several endodontical problems. The results of experimental research targeted to investigate an effect of such combined YAG:Nd and YAG:Cr; Tm; Ho laser parameters like: wavelength, energy density, average power and etc., to oral cavity bacteria deactivation are given finally.

  19. The effect of hydrogen absorption on the structural, electronic and magnetic properties of the C15 Friauf-Laves phase compounds CeFe2, CeRu2 and LaRu2 : an x-ray absorption spectroscopy (XAS) study

    International Nuclear Information System (INIS)

    Chaboy, J.; Garcia, J.; Marcelli, A.

    1995-08-01

    An x-ray absorption spectroscopy (XAS) investigation of the structural changes occurred upon hydriding in the Friauf-Laves phase compounds CeFe 2 , CeRu 2 and LaRu 2 compounds is presented. The analysis of the extended x-ray absorption spectroscopy (EXAFS) spectra at the L-edges of the rare-earth and at the Fe K-edge indicates that the hydrogenation process leads to the suppression of the long-range crystalline order in all the hydride derivates investigated, as well as the different influence of H 2 in both the rare earth and transition metal sublattices. The correlation between the structural and magnetic changes induced by the hydrogen in the lost matrix is discussed in terms of the modification of the electronic properties, i.e., intermediate-valence of Ce, and of the hybridization between the transition metal and rare-earth

  20. The Effect of Phonon Relaxation Process on Absorption Spectra ...

    African Journals Online (AJOL)

    In this work we study the effect of phonon relaxation process on the absorption spectra using the Green's function technique. The Green's function technique which is widely used in many particle problems is used to solve the Kubo formula which describes the optical absorption process. Finally the configurational diagram is ...

  1. Vacuum ultraviolet (VUV) absorption spectra of chromatin and its components

    International Nuclear Information System (INIS)

    Dodonova, N.Y.; Kiseleva, M.N.; Petrov, M.Y.; Tsyganenko, N.M.; Bubyakina, V.V.; Chikhirzhina, G.I.

    1984-01-01

    The electron absorption spectra of thin films of chromatin and chromatin components in the ultraviolet region (140-280 nm) were investigated. The absorption coefficients μ(lambda) of chromatin, nucleosomes with and without histone H1, total histones (TH), and DNA were compared. The spectra of nucleosomes differ from the sum-spectrum of DNA plus TH. The chromatin and nucleosome spectra are not similar in the spectral region of 190-160 nm. The lack of additivity of absorption coefficients at different wavelengths may be explained by different conformational changes of DNA, TH in nucleosomes and chromatin during the process of drying aqueous solutions for the preparation of thin films. The μ(lambda) values are useful for an estimate of the DNA and TH absorption in chromatin and nucleosomes in discussing UV and VUV irradiation damages. (Auth.)

  2. Soft x-ray absorption spectra of ilmenite family.

    Science.gov (United States)

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

    2001-03-01

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

  3. Use of X-Ray Absorption Spectra as a ``Fingerprint'' of the Local Environment in Complex Chalcogenides

    Science.gov (United States)

    Branci, C.; Womes, M.; Lippens, P. E.; Olivier-Fourcade, J.; Jumas, J. C.

    2000-03-01

    The local environment of tin, titanium, iron, and sulfur in spinel compounds Cu2FeSn3S8 and Cu2FeTi3S8 was studied by X-ray absorption spectroscopy (XAS) at the titanium, iron, sulfur K edges, and the tin LI-edge. As detailed calculations of the electronic structure of these compounds are difficult to carry out due to the large number of atoms contained in the unit cell, the XAS spectra of the spinels are compared to those of relatively simple binary sulfides like SnS2, TiS2, and FeS. Indeed, the metal environments in these binary compounds are very similar to those in the spinels, and they can be considered good model compounds allowing the interpretation of electronic transitions observed in the spectra of quaternary phases. In the latter, the bottom of the conduction band is mainly formed by Sn 5s-S 3p, Sn 5p-S 3p antibonding states for the tin-based compounds and by Ti 3dt2g-S 3p, Ti 3deg-S 3p antibonding states for the titanium-based compounds. It it shown that the local environment of iron atoms remains unchanged when substituting tin with titanium atoms, according to a topotactic substitution.

  4. K- and L-edge X-ray Absorption Spectroscopy (XAS) and Resonant Inelastic X-ray Scattering (RIXS) Determination of Differential Orbital Covalency (DOC) of Transition Metal Sites.

    Science.gov (United States)

    Baker, Michael L; Mara, Michael W; Yan, James J; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I

    2017-08-15

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

  5. Probing molecular chirality by coherent optical absorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Jia, W. Z. [Quantum Optoelectronics Laboratory, School of Physics and Technology, Southwest Jiaotong University, Chengdu 610031 (China); Wei, L. F. [Quantum Optoelectronics Laboratory, School of Physics and Technology, Southwest Jiaotong University, Chengdu 610031 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2011-11-15

    We propose an approach to sensitively probe the chirality of molecules by measuring their coherent optical-absorption spectra. It is shown that quantum dynamics of the cyclic three-level chiral molecules driven by appropriately designed external fields is total-phase dependent. This will result in chirality-dependent absorption spectra for the probe field. As a consequence, the charality-dependent information in the spectra (such as the locations and relative heights of the characteristic absorption peaks) can be utilized to identify molecular chirality and determinate enantiomer excess (i.e., the percentages of different enantiomers). The feasibility of the proposal with chiral molecules confined in hollow-core photonic crystal fiber is also discussed.

  6. X-Ray Absorption Spectra of Water from First Principles Calculations

    International Nuclear Information System (INIS)

    Prendergast, David; Galli, Giulia

    2006-01-01

    We present a series of ab initio calculations of the x-ray absorption cross section (XAS) of ice and liquid water at ambient conditions. Our results show that all available experimental data and theoretical results are consistent with the standard model of the liquid as comprising molecules with approximately four hydrogen bonds. Our simulations of ice XAS including the lowest lying excitonic state are in excellent agreement with experiment and those of a quasitetrahedral model of water are in reasonable agreement with recent measurements. Hence we propose that the standard, quasitetrahedral model of water, although approximate, represents a reasonably accurate description of the local structure of the liquid

  7. Valence-to-core-detected X-ray absorption spectroscopy

    DEFF Research Database (Denmark)

    Hall, Eleanor R.; Pollock, Christopher J.; Bendix, Jesper

    2014-01-01

    X-ray absorption spectroscopy (XAS) can provide detailed insight into the electronic and geometric structures of transition-metal active sites in metalloproteins and chemical catalysts. However, standard XAS spectra inherently represent an average contribution from the entire coordination...... environment with limited ligand selectivity. To address this limitation, we have investigated the enhancement of XAS features using valence-to-core (VtC)-detected XAS, whereby XAS spectra are measured by monitoring fluorescence from valence-to-core X-ray emission (VtC XES) events. VtC emission corresponds...... to transitions from filled ligand orbitals to the metal 1s core hole, with distinct energetic shifts for ligands of differing ionization potentials. VtC-detected XAS data were obtained from multiple valence emission features for a series of well-characterized Mn model compounds; taken together, these data...

  8. A Simple Demonstration of Absorption Spectra Using Tungsten Holiday Lights

    Science.gov (United States)

    Birriel, Jennifer J.

    2009-01-01

    In a previous paper submitted to the Demonstrations section (Birriel 2008, "Astronomy Education Review," 7, 147), I discussed using commercially available incandescent light bulbs for the purpose of demonstrating absorption spectra in the classroom or laboratory. This demonstration solved a long-standing problem that many of astronomy instructors…

  9. Theoretical x-ray absorption investigation of high pressure ice and compressed graphite

    International Nuclear Information System (INIS)

    Shaw, Dawn M; Tse, John S

    2007-01-01

    The x-ray absorption spectra (XAS) of high pressure ices II, VIII, and IX have been computed with the Car-Parrinello plane wave pseudopotential method. XAS for the intermediate structures obtained from uniaxial compression of hexagonal graphite along the c-axis are also studied. Whenever possible, comparisons to available experimental results are made. The reliability of the computational methods for the XAS for these structures is discussed

  10. Soft X-ray Absorption Spectroscopy of Liquids and Solutions.

    Science.gov (United States)

    Smith, Jacob W; Saykally, Richard J

    2017-12-13

    X-ray absorption spectroscopy (XAS) is an electronic absorption technique for which the initial state is a deeply buried core level. The photon energies corresponding to such transitions are governed primarily by the binding energies of the initial state. Because the binding energies of core electrons vary significantly among atomic species, this makes XAS an element-selective spectroscopy. Proper interpretation of XA spectra can provide detailed information on the local chemical and geometric environment of the target atom. The introduction of liquid microjet and flow cell technologies into XAS experiments has enabled the general study of liquid samples. Liquids studied to date include water, alcohols, and solutions with relevance to biology and energy technology. This Review summarizes the experimental techniques employed in XAS studies of liquid samples and computational methods used for interpretation of the resulting spectra and summarizes salient experiments and results obtained in the XAS investigations of liquids.

  11. Theory of X-ray absorption and emission spectra

    International Nuclear Information System (INIS)

    Mukoyama, Takeshi

    2004-01-01

    Theoretical studies on X-ray absorption and emission spectroscopy are discussed. Simple expressions for X-ray emission rate and X-ray absorption cross section are presented in the dipole approximation. Various atomic models to obtain realistic wave functions and theoretical calculations for X-ray absorption cross sections and X-ray emission rates are described. In the case of molecules and solids, molecular orbital methods for electronic structures and molecular wave functions are discussed. The emphasis is on the procedures to obtain the excited-state and continuum wave functions for molecules and to calculate the multi-center dipole matrix elements. The examples of the calculated X-ray absorption and emission spectra are shown and compared with the experimental results

  12. Resonant photoionization absorption spectra of spherical quantum dots

    CERN Document Server

    Bondarenko, V

    2003-01-01

    We study theoretically the mid-infrared photon absorption spectra due to bound-free transitions of electrons in individual spherical quantum dots. It is established that change of the dot size in one or two atomic layers or/and number of electrons by one or two can change the peak value of the absorption spectra in orders of magnitude and energy of absorbed photons by tens of millielectronvolts. The reason for this is the formation of specific free states, called resonance states. Numerical calculations are performed for quantum dots (QDs) with radius varying up to 200 A, and one to eight electrons occupying the two lowest bound states. It is supposed that realistic QD systems with resonance states would be of much advantage to design novel infrared QD photo-detectors.

  13. Gigahertz-peaked Spectra Pulsars and Thermal Absorption Model

    Energy Technology Data Exchange (ETDEWEB)

    Kijak, J.; Basu, R.; Lewandowski, W.; Rożko, K. [Janusz Gil Institute of Astronomy, University of Zielona Góra, ul. Z. Szafrana 2, PL-65-516 Zielona Góra (Poland); Dembska, M., E-mail: jkijak@astro.ia.uz.zgora.pl [DLR Institute of Space Systems, Robert-Hooke-Str. 7 D-28359 Bremen (Germany)

    2017-05-10

    We present the results of our radio interferometric observations of pulsars at 325 and 610 MHz using the Giant Metrewave Radio Telescope. We used the imaging method to estimate the flux densities of several pulsars at these radio frequencies. The analysis of the shapes of the pulsar spectra allowed us to identify five new gigahertz-peaked spectra (GPS) pulsars. Using the hypothesis that the spectral turnovers are caused by thermal free–free absorption in the interstellar medium, we modeled the spectra of all known objects of this kind. Using the model, we were able to put some observational constraints on the physical parameters of the absorbing matter, which allows us to distinguish between the possible sources of absorption. We also discuss the possible effects of the existence of GPS pulsars on future search surveys, showing that the optimal frequency range for finding such objects would be from a few GHz (for regular GPS sources) to possibly 10 GHz for pulsars and radio magnetars exhibiting very strong absorption.

  14. Optical absorption and scattering spectra of pathological stomach tissues

    Science.gov (United States)

    Giraev, K. M.; Ashurbekov, N. A.; Lakhina, M. A.

    2011-03-01

    Diffuse reflection spectra of biotissues in vivo and transmission and reflection coefficients for biotissues in vitro are measured over 300-800 nm. These data are used to determine the spectral absorption and scattering indices and the scattering anisotropy factor for stomach mucous membranes under normal and various pathological conditions (chronic atrophic and ulcerous defects, malignant neoplasms). The most importan tphysiological (hemodynamic and oxygenation levels) and structural-morphological (scatterer size and density) parameters are also determined. The results of a morphofunctional study correlate well with the optical properties and are consistent with data from a histomorphological analysis of the corresponding tissues.

  15. Pair Natural Orbital Restricted Open-Shell Configuration Interaction (PNO-ROCIS) Approach for Calculating X-ray Absorption Spectra of Large Chemical Systems.

    Science.gov (United States)

    Maganas, Dimitrios; DeBeer, Serena; Neese, Frank

    2018-02-08

    In this work, the efficiency of first-principles calculations of X-ray absorption spectra of large chemical systems is drastically improved. The approach is based on the previously developed restricted open-shell configuration interaction singles (ROCIS) method and its parametrized version, based on a density functional theory (DFT) ground-state determinant ROCIS/DFT. The combination of the ROCIS or DFT/ROCIS methods with the well-known machinery of the pair natural orbitals (PNOs) leads to the new PNO-ROCIS and PNO-ROCIS/DFT variants. The PNO-ROCIS method can deliver calculated metal K-, L-, and M-edge XAS spectra orders of magnitude faster than ROCIS while maintaining an accuracy with calculated spectral parameters better than 1% relative to the original ROCIS method (referred to as canonical ROCIS). The method is of a black box character, as it does not require any user adjustments, while it scales quadratically with the system size. It is shown that for large systems, the size of the virtual molecular orbital (MO) space is reduced by more than 90% with respect to the canonical ROCIS method. This allows one to compute the X-ray absorption spectra of a variety of large "real-life" chemical systems featuring hundreds of atoms using a first-principles wave-function-based approach. Examples chosen from the fields of bioinorganic and solid-state chemistry include the Co K-edge XAS spectrum of aquacobalamin [H 2 OCbl] + , the Fe L-edge XAS spectrum of deoxymyoglobin (DMb), the Ti L-edge XAS spectrum of rutile TiO 2 , and the Fe M-edge spectrum of α-Fe 2 O 3 hematite. In the largest calculations presented here, molecules with more than 700 atoms and cluster models with more than 50 metal centers were employed. In all the studied cases, very good to excellent agreement with experiment is obtained. It will be shown that the PNO-ROCIS method provides an unprecedented performance of wave-function-based methods in the field of computational X-ray spectroscopy.

  16. Synchrotron radiation based analytical techniques (XAS and XRF)

    International Nuclear Information System (INIS)

    Jha, Shambhu Nath

    2014-01-01

    A brief description of the principles of X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF) techniques is given in this article with emphasis on the advantages of using synchrotron radiation-based instrumentation/beamline. XAS technique is described in more detail to emphasize the strength of the technique as a local structural probe. (author)

  17. Absorption spectra of adenocarcinoma and squamous cell carcinoma cervical tissues

    Science.gov (United States)

    Ivashko, Pavlo; Peresunko, Olexander; Zelinska, Natalia; Alonova, Marina

    2014-08-01

    We studied a methods of assessment of a connective tissue of cervix in terms of specific volume of fibrous component and an optical density of staining of connective tissue fibers in the stroma of squamous cancer and cervix adenocarcinoma. An absorption spectra of blood plasma of the patients suffering from squamous cancer and cervix adenocarcinoma both before the surgery and in postsurgical periods were obtained. Linear dichroism measurements transmittance in polarized light at different orientations of the polarization plane relative to the direction of the dominant orientation in the structure of the sample of biotissues of stroma of squamous cancer and cervix adenocarcinoma were carried. Results of the investigation of the tumor tissues showed that the magnitude of the linear dichroism Δ is insignificant in the researched spectral range λ=280-840 nm and specific regularities in its change observed short-wave ranges.

  18. Infrared absorption spectra of selenate compounds of indium (3)

    International Nuclear Information System (INIS)

    Kharitonov, Yu.Ya.; Kadoshnikova, N.V.; Tananaev, I.V.

    1979-01-01

    Obtained and discussed are infrared absorption spectra (400-4000 cm -1 ) of the following indium selenates: In 2 (SeO 4 ) 3 x5H 2 O, In 2 (SeO 4 ) 3 x9H 2 O, NaIn(SeO 4 ) 2 x6H 2 O, NaIn(SeO 4 ) 2 xH 2 O, MIn(SeO 4 ) 2 x4H 2 O (M=NH 4 , K, Rb), CsIn(SeO 4 ) 2 x2H 2 O, Na 3 In(SeO 4 ) 3 x7H 2 O, MIn(SeO 4 ) 2 (M=NH 4 , Na, K, Rb, Cs), M 2 InOH(SeO 4 ) 2 xyH 2 O (M=NH 4 , Na, K, Rb) and K 2 InOD(SeO 4 ) 2 xyD 2 O

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

    Science.gov (United States)

    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.

  20. Absorption spectra analysis of hydrated uranium(III) complex chlorides

    Science.gov (United States)

    Karbowiak, M.; Gajek, Z.; Drożdżyński, J.

    2000-11-01

    Absorption spectra of powdered samples of hydrated uranium(III) complex chlorides of the formulas NH 4UCl 4 · 4H 2O and CsUCl 4 · 3H 2O have been recorded at 4.2 K in the 4000-26 000 cm -1 range. The analysis of the spectra enabled the determination of crystal-field parameters and assignment of 83 and 77 crystal-field levels for the tetrahydrate and trihydrate, respectively. The energies of the levels were computed by applying a simplified angular overlap model as well as a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions. Ab initio calculations have enabled the application of a simplified parameterization and the determination of the starting values of the AOM parameters. The received results have proved that the AOM approach can quite well predict both the structure of the ground multiplet and the positions of the crystal-field levels in the 17 000-25 000 cm -1 range, usually obscured by strong f-d bands.

  1. Substitution effects on the absorption spectra of nitrophenolate isomers.

    Science.gov (United States)

    Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

    2012-10-05

    Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

  2. Linear optical absorption spectra of mesoscopic structures in intense THz fields: Free-particle properties

    DEFF Research Database (Denmark)

    Johnsen, Kristinn; Jauho, Antti-Pekka

    1998-01-01

    We theoretically study the effect of THz radiation on the linear optical absorption spectra of semiconductor structures. A general theoretical framework, based on nonequilibrium Green functions, is formulated and applied to the calculation of linear optical absorption spectrum for several...

  3. Molecular absorption spectra of beryllium, cerium, lanthanum, iron, and platinum salts

    International Nuclear Information System (INIS)

    Daidoji, Hidehiro

    1980-01-01

    The absorption spectra of some salts of beryllium, cerium, lanthanum, iron and platinum in air-acetylene flame were measured in the wavelength range from 200 to 400 nm. A Hitachi 207 type atomic absorption spectrophotometer was used. A deuterium lamp, a home-made continuous radiation lamp and some hollow cathode lamps were used as light sources. The new molecular absorption spectra of cerium, lanthanum and platinum and the absorption spectra due to Be(OH) 2 , LaO, PtH, FeO and FeCl in 200-400 nm region were obtained. Emission spectra of CeO, LaO and FeOH were also obtained. These molecular absorption bands were estimated as absorption errors of maximum 15 times to the sensitivity of each elements in atomic absorption spectrometry. In addition, spectral line interferences of iron were observed in atomic absorption spectrometry of Zn, Cd, Ni, Cu and Cr. (author)

  4. The TApIR experiment. IR absorption spectra of liquid hydrogen isotopologues

    International Nuclear Information System (INIS)

    Groessle, Robin

    2015-01-01

    The scope of the thesis is the infrared absorption spectroscopy of liquid hydrogen isotopologues with the tritium absorption infrared spectroscopy (TApIR) experiment at the tritium laboratory Karlsruhe (TLK). The calibration process from the sample preparation to the reference measurements are described. A further issue is the classical evaluation of FTIR absorption spectra and the extension using the rolling circle filter (RCF) including the effects on statistical and systematical errors. The impact of thermal and nuclear spin temperature on the IR absorption spectra is discussed. An empirical based modeling for the IR absorption spectra of liquid hydrogen isotopologues is performed.

  5. An Inverse Modeling Approach to Estimating Phytoplankton Pigment Concentrations from Phytoplankton Absorption Spectra

    Science.gov (United States)

    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.

  6. Infrared absorption spectra of various doping states in cuprate superconductors

    International Nuclear Information System (INIS)

    Yonemitsu, K.; Bishop, A.R.; Lorenzana, J.

    1992-01-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs

  7. Computer simulation of molecular absorption spectra for asymmetric top molecules

    International Nuclear Information System (INIS)

    Bende, A.; Tosa, V.; Cosma, V.

    2001-01-01

    The effective Hamiltonian formalism has been used to develop a model for infrared multiple-photon absorption (IRMPA) process in asymmetric top molecules. Assuming a collisionless regime, the interaction between the molecule and laser field can be described by the time-dependent Schroedinger equation. By using the rotating wave approximation and Laplace transformation, the time-dependent problem reduces to a time-independent eigen problem for an effective Hamiltonian which can be solved only numerically for a real vibrational-rotational structure of polyatomic molecule. The vibrational-rotational structure is assumed to be an anharmonic oscillator coupled to an asymmetric rigid rotor. The main assumptions taken into account for this model are the following: (1) the excitation is coherent, i.e. the collision (if present during the laser pulse) does not influence the excitation; (2) the excitation starts from the ground state and is near resonant to a normal mode, thus, the rotating wave approximation can be applied; (3) after absorbing N photons the vibrational energy of the excited mode leak into a quasicontinuum; (4) the thermal population of the ground state is given by the Maxwell-Boltzmann distribution law. The energy levels of the asymmetric top molecules cannot be represented by an explicit formula analogous to that for the symmetric top, according to quantum mechanics, but we can consider it a deviation from the prolate or oblate case of the symmetric top, and we can find in the same manner the selection rules of the asymmetric case using the selection rules for the symmetric case. The infrared bands of asymmetric top molecules are not resolved, but if the dispersion used is not too small, so that the envelopes of the bands can be distinguished from simple maxima, it is possible to draw conclusions as to the type of the bands. In this case, the simulation of the absorption spectra can give us some important information about the types of these bands. In

  8. Recommendations for the presentation of infrared absorption spectra in data collections condensed phases

    CERN Document Server

    Becker, E D

    2013-01-01

    Recommendations for the Presentation of Infrared Absorption Spectra in Data Collections-A. Condensed Phases presents the recommendations related to the infrared spectra of condensed phase materials that are proposed for permanent retention in data collections. These recommendations are based on two reports published by the Coblentz Society. This book emphasizes the three levels of quality evaluation for infrared spectra as designated by the Coblentz Society, including critically defined physical data, research quality analytical spectra, and approved analytical spectra. This text discusses the

  9. A study of luminescence and absorption spectra of GaP

    International Nuclear Information System (INIS)

    Mansour, H.M.M.; Abdel Wahab, S.M.

    1994-08-01

    Experimental luminescence and absorption spectra of GaP at room temperature are presented. A theoretical analysis has been performed on the luminescence and absorption spectra in GaP. The experimental data are in good agreement with the theoretical results. (author). 18 refs, 8 figs

  10. X-ray Absorption Spectroscopy of the Rare Earth orthophosphates

    International Nuclear Information System (INIS)

    Shuh, D.K.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-06-01

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d 10 4f n → 3d- 9 4f n+1 transitions and these transitions exhibit a wealth of spectroscopic features. The XAS measurements of single crystal REPO 4 (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) at the 3d edge were performed in the total yield mode at beam line 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble the XAS of the corresponding RE metal. This is not unexpected and emphasizes the major contribution of the trivalent state to the electronic transitions at the RE 3d edges. These spectra unequivocally identify the transitions originating from well-characterized RE cores and correlate well with previous theoretical investigations

  11. Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters using Density Functional Theory

    Science.gov (United States)

    2017-05-05

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9724 Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters...TELEPHONE NUMBER (include area code) b. ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Equilibrium Structures and Absorption...and electronic excited-state absorption spectra for eqilibrium structures of SixOy molecular clusters using density function theory (DFT) and time

  12. Fourier Transform and Photoacoustic Absorption Spectra of Ethylene within 6035 6210 cm-1: Comparative Measurements

    International Nuclear Information System (INIS)

    Kapitanov, V.A.; Solodov, A.M.; Petrova, T.M.; Ponomarev, Y.N.

    2010-01-01

    Measurements of ethylene absorption spectra with Fourier Transform (FT) and Photoacoustic (PA) spectrometers within 6035-6210 cm -1 are described. The methodology used for building the frequency scale for both spectrometers is presented. The methane absorption spectrum, included into the HITRAN database, was used in both cases to calibrate the frequency scale. Ethylene absorption spectra were obtained with the two recording methods; a coincidence of the measured line center positions was obtained with an accuracy of 0.0005 cm -1

  13. COLORED DISSOLVED ORGANIC MATTER (CDOM) CHARACTERIZATION BY ABSORPTION AND FLUORESCENCE SPECTRA

    OpenAIRE

    Goncalves Araujo, Rafael; Ramirez-Perez, Marta; Kraberg, Alexandra; Piera, Jaume; Bracher, Astrid

    2014-01-01

    Colored dissolved organic matter (CDOM) absorption and fluorescence spectra were analyzed from samples collected in the Lena River Delta region (Siberia, Russia; summer-2013) and in the Alfacs Bay (Ebro River Delta, Spain; summer-2013/winter-2014) in order to use optical measurements to infer loading and origin of CDOM. Absorbance spectra and Excitation-Emission matrices (EEMs) were obtained with a HORIBA Aqualog® spectrofluorometer. CDOM absorption at 443nm (a443) and terrestrial absorption ...

  14. Linear and nonlinear optical absorption coefficients in GaAs/Ga{sub 1-x}Al{sub x}As concentric double quantum rings: Effects of hydrostatic pressure and aluminum concentration

    Energy Technology Data Exchange (ETDEWEB)

    Baghramyan, H.M. [Department of Solid State Physics, Yerevan State University, Al. Manookian 1, 0025 Yerevan (Armenia); Barseghyan, M.G., E-mail: mbarsegh@ysu.am [Department of Solid State Physics, Yerevan State University, Al. Manookian 1, 0025 Yerevan (Armenia); Kirakosyan, A.A. [Department of Solid State Physics, Yerevan State University, Al. Manookian 1, 0025 Yerevan (Armenia); Restrepo, R.L. [Escuela de Ingenieria de Antioquia, AA 7516 Medellin (Colombia); Duque, C.A. [Instituto de Fisica, Universidad de Antioquia, AA 1226 Medellin (Colombia)

    2013-02-15

    The linear and nonlinear intra-band optical absorption coefficients in GaAs/Ga{sub 1-x}Al{sub x}As two-dimensional concentric double quantum rings are investigated. Taking into account the combined effects of hydrostatic pressure and aluminum concentration the energies of the ground (n=1,l=0) and the first excited state (n=2,l=1) have been found using the effective mass approximation and the transfer matrix formalism. The energies of these states and the corresponding threshold energy of the intra-band optical transitions are examined as a function of hydrostatic pressure and aluminum concentration for different sizes of the structure. We also investigated the dependencies of the linear, nonlinear, and total optical absorption coefficients as functions of the incident photon energy for different values of hydrostatic pressure, aluminum concentration, sizes of the structure, and incident optical intensity. Its is found that the effects of the hydrostatic pressure and the aluminum concentration lead to a shifting of the resonant peaks of the intra-band optical spectrum. - Highlights: Black-Right-Pointing-Pointer Linear and nonlinear intra-band absorption in quantum rings. Black-Right-Pointing-Pointer Threshold energy strongly depends on the hydrostatic pressure. Black-Right-Pointing-Pointer Threshold energy strongly depends on the stoichiometry and sizes of structure. Black-Right-Pointing-Pointer Optical absorption is affected by the incident optical intensity.

  15. XAS and XMCD investigation of Mn12 monolayers on gold.

    Science.gov (United States)

    Mannini, Matteo; Sainctavit, Philippe; Sessoli, Roberta; Cartier dit Moulin, Christophe; Pineider, Francesco; Arrio, Marie-Anne; Cornia, Andrea; Gatteschi, Dante

    2008-01-01

    The deposition of Mn(12) single molecule magnets on gold surfaces was studied for the first time using combined X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) methods at low temperature. The ability of the proposed approach to probe the electronic structure and magnetism of Mn(12) complexes without significant sample damage was successfully checked on bulk samples. Detailed information on the oxidation state and magnetic polarization of manganese ions in the adsorbates was obtained from XAS and XMCD spectra, respectively. Partial reduction of metal ions to Mn(II) was clearly observed upon deposition on Au(111) of two different Mn(12) derivatives bearing 16-acetylthio-hexadecanoate and 4-(methylthio)benzoate ligands. The average oxidation state, as well as the relative proportions of Mn(II), Mn(III) and Mn(IV) species, are strongly influenced by the deposition protocol. Furthermore, the local magnetic polarizations are significantly decreased as compared with bulk Mn(12) samples. The results highlight an utmost redox instability of Mn(12) complexes at gold surfaces, presumably accompanied by structural rearrangements, which cannot be easily revealed by standard surface analysis based on X-ray photoelectron spectroscopy and scanning tunnelling microscopy.

  16. Urbach tails in the absorption spectra of semiconducting molybdenum-borate glasses

    International Nuclear Information System (INIS)

    Jamel Basha Adlan, M.; Wan Yusri Wan Yusuff; Tan, C.W.; Yam, F.K.

    1991-01-01

    The absorption curve of many amorphous compound semiconductors may be divided into three regions: (1) the high absorption region (α(w)≥10 4 cm -1 ), (2) an exponential region (1cm -1 ≤(w)≤10 4 cm -1 ) which obeys Urbach's rule and (3) a weak absorption tail (α(w)≤1cm -1 ). In this paper we will present the absorption edge of binary Molybdenum-Borate glasses at the exponential region of the spectra

  17. Identification of Metal Absorption Lines on Quasar Spectra of SDSS ...

    Indian Academy of Sciences (India)

    . Baise 533000, China. 2Guangdong University of Technology, Guangzhou 510006, China. 3Centre for Astrophysics, Guangzhou University, Guangzhou 510006, China. ∗ e-mail: cysu@gdut.edu.cn. Abstract. Absorption lines are an important ...

  18. Photoluminescence and absorption spectra of various common TL phosphors - interpretation of TL mechanisms

    International Nuclear Information System (INIS)

    Nagpal, J.S.

    1980-01-01

    Photoluminescence and absorption spectra of TL phosphors TLD-100, CaF 2 :Dy, CaSO 4 :Dy(0.05%wt), CaSO 4 :Tm(0.05%wt) and Mg 2 SiO 4 :Tb have been measured. The absorption spectra are typical of RE 2+ in rare earth doped irradiated phosphors. On heating RE 2+ yields RE 3+ and emission from the excited states of RE 3+ is observed. (author)

  19. Absorption spectra of ammonia near 1 mu m

    Czech Academy of Sciences Publication Activity Database

    Barton, E. J.; Polyansky, O. L.; Yurchenko, S. N.; Tennyson, J.; Civiš, Svatopluk; Ferus, Martin; Hargreaves, R.; Ovsyannikov, R. I.; Kyuberis, A. A.; Zobov, N. F.; Béguier, S.; Campargue, A.

    2017-01-01

    Roč. 203, DEC 2017 (2017), s. 392-397 ISSN 0022-4073 EU Projects: European Commission(XE) 267219 - EXOMOL Grant - others:RFBR(RU) 16-32-00244 Institutional support: RVO:61388955 Keywords : room temperature * ammonia * absorption intensities * FTIR spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.419, year: 2016

  20. Donor impurity-related linear and nonlinear optical absorption coefficients in GaAs/Ga{sub 1−x}Al{sub x}As concentric double quantum rings: Effects of geometry, hydrostatic pressure, and aluminum concentration

    Energy Technology Data Exchange (ETDEWEB)

    Baghramyan, H.M.; Barseghyan, M.G.; Kirakosyan, A.A. [Department of Solid State Physics, Yerevan State University, Al. Manookian 1, 0025 Yerevan (Armenia); Restrepo, R.L. [Física Teórica y Aplicada, Escuela de Ingeniería de Antioquia, AA 7516, Medellín (Colombia); Grupo de Materia Condensada-UdeA, Instituto de Física, Facultadde Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21,Medellín (Colombia); Mora-Ramos, M.E. [Grupo de Materia Condensada-UdeA, Instituto de Física, Facultadde Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21,Medellín (Colombia); Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, CP 62209, Cuernavaca, Morelos (Mexico); Duque, C.A., E-mail: cduque@fisica.udea.edu.co [Grupo de Materia Condensada-UdeA, Instituto de Física, Facultadde Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21,Medellín (Colombia)

    2014-01-15

    The linear and nonlinear optical absorption associated with the transition between 1s and 2s states corresponding to the electron-donor-impurity complex in GaAs/Ga{sub 1−x}Al{sub x}As three-dimensional concentric double quantum rings are investigated. Taking into account the combined effects of hydrostatic pressure and the variation of the aluminum concentration, the energies of the ground and first excited s-like states of a donor impurity in such a system have been calculated using the effective mass approximation and a variational method. The energies of these states and the corresponding threshold energy of the optical transitions are examined as functions of hydrostatic pressure, aluminum concentration, radial impurity position, as well as the geometrical dimensions of the structure. The dependencies of the linear, nonlinear and total optical absorption coefficients as functions of the incident photon energy are investigated for different values of those mentioned parameters. It is found that the influences mentioned above lead to either redshifts or blueshifts of the resonant peaks of the optical absorption spectrum. It is particularly discussed the unusual property exhibited by the third-order nonlinear of becoming positive for photon energies below the resonant transition one. It is shown that this phenomenon is associated with the particular features of the system under study, which determine the values of the electric dipole moment matrix elements. -- Highlights: • Intra-band optical absorption associated to impurity states in double quantum rings. • Combined effects of hydrostatic pressure and aluminum concentration are studied. • The influences mentioned above lead to shifts of resonant peaks. • It is discussed an unusual property exhibited by the third-order nonlinear absorption.

  1. Invisible structures in the X-ray absorption spectra of actinides

    NARCIS (Netherlands)

    Kvashnina, Kristina O.; De Groot, Frank M F

    The X-ray absorption spectra of actinides are discussed with an emphasis on the fundamental effects that influence their spectral shape, including atomic multiplet theory, charge transfer theory and crystal field theory. Many actinide spectra consist of a single peak and it is shown that the use of

  2. Optical absorption spectra of linear and cyclic thiophenes--selection rules manifestation

    International Nuclear Information System (INIS)

    Bednarz, Mariusz; Reineker, Peter; Mena-Osteritz, Elena; Baeuerle, Peter

    2004-01-01

    We theoretically study the size-dependent relation between absorption spectra of thiophene-based oligomers and the corresponding cyclothiophenes. In our approach based on a Frenkel exciton Hamiltonian, we demonstrate that the geometry and selection rules determine the observed relations between the spectra

  3. Absorption Spectra Of Rbcl:Yb Rbbr:Yb And Rbi:Yb Crystals ...

    African Journals Online (AJOL)

    Single crystals of rubidium chloride, bromide and iodide were doped with substitutional divalent ytterbium, Yb ions, by heating them in ytterbium atmosphere. The absorption spectra of the Yb doped crystals were measured at room and liquid nitrogen temperatures. The spectra were found to consist of intense broad ...

  4. Absorption in the spectra of quasi stellar objects and BL Lac objects

    International Nuclear Information System (INIS)

    Perry, J.J.; Burbidge, E.M.; Burbidge, G.R.

    1978-06-01

    An extensive review is given of the observations of absorption in the spectra of QSOs and BL Lac objects. In Table Ia we summarize all of the information available up to May 1, 1978 on objects which show absorption. Following discussion of the observations in Section II, possible interpretations are critically discussed. (orig.) [de

  5. SPECTROPHOTOMETRY OF HEMOGLOBIN - ABSORPTION-SPECTRA OF RAT OXYHEMOGLOBIN, DEOXYHEMOGLOBIN, CARBOXYHEMOGLOBIN, AND METHEMOGLOBIN

    NARCIS (Netherlands)

    ZIJLSTRA, WG; BUURSMA, A; FALKE, HE; CATSBURG, JF

    The absorptivity at 540 nm of methemoglobincyanide from rat blood was determined on the basis of iron and found to be equal to the established value for human methemoglobincyanide (11,01/mmol/cm). On this basis the absorption spectra of the common derivatives were determined for rat hemoglobin.

  6. Spectrophotometry of hemoglobin : Absorption spectra of bovine oxyhemoglobin, deoxyhemoglobin, carboxyhemoglobin, and methemoglobin

    NARCIS (Netherlands)

    Zijlstra, WG; Buursma, A

    1997-01-01

    The absorptivity at 540 nm of bovine hemiglobincyanide (cyanmethemoglobin) was determined on the basis of the iron content and found to be equal to the established value for human hemiglobincyanide (11.0 L . mmol(-1).cm(-1)). On this basis the absorption spectra of the common derivatives were

  7. Particulate absorption properties in the Red Sea from hyperspectral particulate absorption spectra

    KAUST Repository

    Tiwari, Surya Prakash; Zarokanellos, Nikolaos; Kheireddine, Malika; Shanmugam, Palanisamy; Jones, Burton

    2018-01-01

    This paper aims to describe the variability of particulate absorption properties using a unique hyperspectral dataset collected in the Red Sea as part of the TARA Oceans expedition. The absorption contributions by phytoplankton (aph) and non

  8. Electronic and oscillation absorption spectra of blood plamsa at surgical diseases of thyroid gland

    Science.gov (United States)

    Guminetskiy, S. G.; Motrich, A. V.; Poliansky, I. Y.; Hyrla, Ya. V.

    2012-01-01

    The results of investigating the absorption spectra of blood plasma in the visible and infrared parts of spectra obtained using the techniques of spherical photometer and spectrophotometric complex "Specord IR75" are presented. The possibility of using these spectra for diagnoses the cases of diffuse toxic goiter and nodular goiter and control of treatment process in postsurgical period in the cases of thyroid gland surgery is estimated.

  9. Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

    International Nuclear Information System (INIS)

    Marcelli, A.; Wu, Z.; Mottana, A.; Giuli, G.; Paris, E.; Seifert, F.

    1996-03-01

    The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells

  10. Effects of higher-coordination shells in garnets detected by XAS at the Al K-edge

    Energy Technology Data Exchange (ETDEWEB)

    Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati (Italy). Lab. Nazionale di Frascati; Wu, Z. [CNRS UMR 110, Laboratoire de Chimie des Solides, Nantes Cedex (France). Institut de materiaux de Nantes; Mottana, A. [Roma III Univ., Rome (Italy). Dipartimento di Scienze Geologiche; Giuli, G.; Paris, E. [Camerino Univ., Camerino (Italy).Diparimento di Scienze della Terra; Seifert, F [Univ. Bayreuth, Bayreuth (Italy). Bayerisches Geoinstitut (Germany)

    1996-03-01

    The aluminium 1 s x-ray-absorption spectra of a series of garnets, pyrope, almandine, spessartine and grossular, are compared to full multiple-scattering calculation using cluster models. An overall good agreement between experiment and calculation, extended also to the edge region,is obtained in the energy range in up to 60 e V above the threshold, provided cluster containing at least 40 atoms are used. The analysis of these garnet XAS spectra provides clear evidence on the effect of probe, XANES spectroscopy at the edge of low Z elements appears to be a perfect tool to investigate the role played by atoms located in higher-coordination shells.

  11. Lifetime-broadening-suppressed X-ray absorption spectrum of β-YbAlB4 deduced from Yb 3d → 2p resonant X-ray emission spectroscopy

    International Nuclear Information System (INIS)

    Kawamura, Naomi; Mizumaki, Masaichiro; Kanai, Noriko; Hayashi, Hisashi; Matsuda, Yasuhiro H.; Kuga, Kentaro; Nakatsuji, Satoru; Watanabe, Shinji

    2017-01-01

    In this work, the Yb 3d → 2p (Yb Lα 1,2 ) resonant X-ray emission spectrum of β-YbAlB 4 was acquired using excitation energies around the Yb L 3 -edge, at 2 K. Subsequently, the lifetime-broadening-suppressed (LBS) X-ray absorption structure (XAS) spectrum was obtained using the SIM-RIXS program. This spectrum was found to exhibit clearly resolved pre-edge and shoulder structures. Resonant Lα 1 emission spectra were well reproduced from LBS-XAS profiles over wide ranges of excitation and emission energies. In contrast, noticeable discrepancies appeared between the experimental and simulated Lα 2 emission spectra, suggesting an effect resulting from M 4 M 5 O 1 Coster-Kronig transitions. LBS-XAS, in conjunction with partial fluorescence yield (PFY) XAS and transmission XAS, determined a value for the Yb valence (v) in β-YbAlB 4 of 2.76 ± 0.08 at 2 K. Despite this relatively large uncertainty in v, each method provided a consistent variation in valence (δv) as the temperature was raised from 2 to 280 K: 0.060 ± 0.004 (LBS-XAS), 0.061 ± 0.005 (PFY-XAS) and 0.058 ± 0.007 (transmission XAS). The smaller δv associated with LBS-XAS demonstrates the greater precision of this method. (author)

  12. Faraday effect and λ-modulation absorption spectra of GaP

    International Nuclear Information System (INIS)

    Petkova, P N; Dimov, T N; Iliev, I A

    2007-01-01

    There are presented the absorption optical spectra of GaP measured by λ-modulation method at room temperature in the spectral region from 505 nm to 700 nm. It is not possible even by λ-modulation to be registered at room temperature the wave bands due to the exciton-phonon interaction. The absorption spectra of GaP carried out by a λ-modulation can be separated exactly in the spectral parts as follows: the transmittance region where the absorption is too slightly expressed; the region determined by the phonon-assisted indirect transitions; the region of the interband absorption. The purpose of Faraday rotation measurements is to establish the influence of the exciton-phonon interaction on the magneto-optical effect. The magneto-optical effect has been investigated by a φ-modulation. The spectral dependence of dn/dλ in the transmittance region is determined by the φ-modulated spectra

  13. Carbon dioxide laser absorption spectra of toxic industrial compounds

    International Nuclear Information System (INIS)

    Loper, G.L.; Sasaki, G.R.; Stamps, M.A.

    1982-01-01

    CO 2 laser absorption cross-section data are reported for acrolein, styrene, ethyl acrylate, trichloroethylene, vinyl bromide, and vinylidene chloride. These data indicate that sub parts per billion level, interference-free detection limits should be possible for these compounds by the CO 2 laser photoacoustic technique. Photoacoustic detectabilities below 40 ppb should be possible for these compounds in the presence of ambient air concentrations of water vapor and other anticipated interferences. These compounds are also found not to be important inerference in the detection of toxic hydrazine-based rocket fuels by CO 2 laser spectroscopic techniques

  14. Monitoring the variability of intrinsic absorption lines in quasar spectra , ,

    International Nuclear Information System (INIS)

    Misawa, Toru; Charlton, Jane C.; Eracleous, Michael

    2014-01-01

    We have monitored 12 intrinsic narrow absorption lines (NALs) in five quasars and seven mini-broad absorption lines (mini-BALs) in six quasars for a period of 4-12 yr (1-3.5 yr in the quasar rest-frame). We present the observational data and the conclusions that follow immediately from them, as a prelude to a more detailed analysis. We found clear variability in the equivalent widths (EWs) of the mini-BAL systems but no easily discernible changes in their profiles. We did not detect any variability in the NAL systems or in narrow components that are often located at the center of mini-BAL profiles. Variations in mini-BAL EWs are larger at longer time intervals, reminiscent of the trend seen in variable BALs. If we assume that the observed variations result from changes in the ionization state of the mini-BAL gas, we infer lower limits to the gas density ∼10 3 -10 5 cm –3 and upper limits on the distance of the absorbers from the central engine of the order of a few kiloparsecs. Motivated by the observed variability properties, we suggest that mini-BALs can vary because of fluctuations of the ionizing continuum or changes in partial coverage while NALs can vary primarily because of changes in partial coverage.

  15. Absorption spectra and speciation of plutonium(VI) with phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Weger, H.T.; Reed, D.

    1996-02-01

    Plutonium(VI)-phosphate species in aqueous solution, at pH < 2.4, formed two species: PuO{sub 2}H{sub 2}PO{sub 4}{sup +} (characterized by an 835 nm absorption band) and the solid phase PuO{sub 2}(H{sub 2}PO{sub 4}){sub 2}. The stability constant {beta} for the PuO{sub 2}H{sub 2}PO{sub 4}{sup +} species was determined to be log {beta} = 2.1 {+-} 0.1 (ionic strength = 0.6--0.9 M) and log {beta}{sup T} = 2.6 {+-} 0.15 (zero ionic strength). Four Pu(VI)-phosphate species (absorption bands at 842, 846, 857, and 866 nm) formed at pH = 2.4 to 12.2 and are characterized by polynuclear behavior, the formation of precipitates, and colloidal properties. The 842 and 846 nm species are believed to be [PuO{sub 2}(HPO{sub 4}){sub m}]{sub n} and [PuO{sub 2}(NaPO{sub 4}){sub m}]{sub n}. The 857 and 866 nm species area as yet unidentified. The speciation of plutonium with phosphate is of interest to radionuclide migration studies because phosphate is present in many groundwaters and may be used as an actinide getter in nuclear waste disposal. An actinide getter is a complexing agent that forms insoluble phases with actinides, thereby reducing their migration.

  16. Terahertz absorption spectra of commonly used antimalarial drugs

    Science.gov (United States)

    Bawuah, Prince; Zeitler, J. Axel; Ketolainen, Jarkko; Peiponen, Kai-Erik

    2018-03-01

    Terahertz (THz) spectra from the pure forms [i.e. the active pharmaceutical ingredients (APIs)] of four commonly used antimalarial drugs are reported. The well-defined spectral fingerprints obtained for these APIs in the spectral range of 0.1 THz-3 THz show the sensitivity of the THz time-domain spectroscopic (THz-TDS) method for screening antimalarial drugs. For identification purpose, two commercially available antimalarial tablets were detected. Clear spectral fingerprints of the APIs in the antimalarial tablets were obtained even amidst the several types of excipients present in the tablets. This observation further proves the high sensitivity of the THz techniques in tracking the presence or absence of API in a pharmaceutical tablet. We envisage that the spectral data obtained for these drugs can contribute to a spectroscopic database in the far infrared spectral region and hence support the modelling of THz sensing to differentiate between genuine and counterfeit antimalarial tablets.

  17. Terahertz absorption spectra of commonly used antimalarial drugs

    Science.gov (United States)

    Bawuah, Prince; Zeitler, J. Axel; Ketolainen, Jarkko; Peiponen, Kai-Erik

    2018-06-01

    Terahertz (THz) spectra from the pure forms [i.e. the active pharmaceutical ingredients (APIs)] of four commonly used antimalarial drugs are reported. The well-defined spectral fingerprints obtained for these APIs in the spectral range of 0.1 THz-3 THz show the sensitivity of the THz time-domain spectroscopic (THz-TDS) method for screening antimalarial drugs. For identification purpose, two commercially available antimalarial tablets were detected. Clear spectral fingerprints of the APIs in the antimalarial tablets were obtained even amidst the several types of excipients present in the tablets. This observation further proves the high sensitivity of the THz techniques in tracking the presence or absence of API in a pharmaceutical tablet. We envisage that the spectral data obtained for these drugs can contribute to a spectroscopic database in the far infrared spectral region and hence support the modelling of THz sensing to differentiate between genuine and counterfeit antimalarial tablets.

  18. Absorption spectra of ammonia near 1 μm

    Science.gov (United States)

    Barton, Emma J.; Polyansky, Oleg L.; Yurchenko, Sergei. N.; Tennyson, Jonathan; Civiš, S.; Ferus, M.; Hargreaves, R.; Ovsyannikov, R. I.; Kyuberis, A. A.; Zobov, N. F.; Béguier, S.; Campargue, A.

    2017-12-01

    An ammonia absorption spectrum recorded at room temperature in the region 8800-10,400 cm-1 is analysed using a variational line list, BYTe, and ground state energies determined using the MARVEL procedure. BYTe is used as a starting point to initialise assignments by combination differences and the method of branches. Assignments are presented for the region 9400-9850 cm-1. 642 lines are assigned to 6 previously unobserved vibrational bands, (2v1 + 2 v42) ±, (2v1 + v31) ± and (v1 + v31 + 2 v42) ±, leading to 428 new energy levels with 208 confirmed by combination differences. A recently calculated purely ab initio NH3 PES is also used to calculate rovibrational energy levels. Comparison with assigned levels shows better agreement between observed and calculated levels than for BYTe for higher vibrational bands.

  19. Effects of UV radiation on the UV-VIS absorption spectra of the EAGLE's medium components

    International Nuclear Information System (INIS)

    Bollmann, G.; Redmann, K.

    1990-01-01

    The impact of ultraviolet light on uv/vis absorption spectra of selected individual components of the cell breeding medium according to Eagle (MEM) was investigated. The strongest alterations of light absorption were detected in L-phenylalanin, L-tyrosin and L-tryptophane. Thus, the absorption behaviour of the Eagle (MEM) medium changed post radiationem may be attributed to spectrophotometric alterations of absorption in aromatic amino acids. The results are discussed with regard to the effect on the surface charge of erythrocytes. (author)

  20. Particulate absorption properties in the Red Sea from hyperspectral particulate absorption spectra

    KAUST Repository

    Tiwari, Surya Prakash

    2018-03-16

    This paper aims to describe the variability of particulate absorption properties using a unique hyperspectral dataset collected in the Red Sea as part of the TARA Oceans expedition. The absorption contributions by phytoplankton (aph) and non-algal particles (aNAP) to the total particulate absorption coefficients are determined using a numerical decomposition method (NDM). The NDM is validated by comparing the NDM derived values of aph and aNAP with simulated values of aph and aNAP are found to be in excellent agreement for the selected wavelengths (i.e., 443, 490, 555, and 676nm) with high correlation coefficient (R2), low root mean square error (RMSE), mean relative error (MRE), and with a slope close to unity. Further analyses showed that the total particulate absorption coefficients (i.e., ap(443)average = 0.01995m−1) were dominated by phytoplankton absorption (i.e., aph(443)average = 0.01743m−1) with a smaller contribution by non-algal particles absorption (i.e., aNAP(443)average = 0.002524m−1). The chlorophyll a is computed using the absorption based Line Height Method (LHM). The derived chlorophyll-specific absorption ((a⁎ph = aph(λ)/ChlLH)) showed more variability in the blue part of spectrum as compared to the red part of spectrum representative of the package effect and changes in pigment composition. A new parametrization proposed also enabled the reconstruction of a⁎ph(λ) for the Red Sea. Comparison of derived spectral constants with the spectral constants of existing models showed that our study A(λ) values are consistent with the existing values, despite there is a divergence with the B(λ) values. This study provides valuable information derived from the particulate absorption properties and its spectral variability and this would help us to determine the relationship between the phytoplankton absorption coefficients and chlorophyll a and its host of variables for the Red Sea.

  1. Continuous registration of optical absorption spectra of periodically produced solvated electrons

    International Nuclear Information System (INIS)

    Krebs, P.

    1975-01-01

    Absorption spectra of unstable intermediates, such as solvated electrons, were usually taken point by point, recording the time-dependent light absorption after their production by a flash. The experimental arrangement for continuous recording of the spectra consists of a conventional one beam spectral photometer with a stabilized white light source, a monochromator, and a light detector. By periodic production of light absorbing intermediates such as solvated electrons, e.g., by ac uv light, a small ac signal is modulated on the light detector output which after amplification can be continuously recorded as a function of wavelength. This method allows the detection of absorption spectra when disturbances from the outside provide a signal-to-noise ratio smaller than 1

  2. Media effects on the optical absorption spectra of silver clusters embedded in rara gas matrices

    International Nuclear Information System (INIS)

    Fedrigo, S.; Harbich, W.; Buttet, J.

    1993-01-01

    The optical absorption of small mass selected Ag n -clusters (n=7, 11, 15, 21) embedded in solid Ar, Kr and Xe has been measured. The absorption spectra show 1 to 3 major peaks between 3 and 4.5 eV, depending on the cluster size. Changing the matrix gas Ar→Kr→Xe induces a redshift which is comparable for all sizes studied and does not affect the main structure of the absorption spectra. We propose a scheme to estimate the gas phase value of the absorption energies which is in fair agreement with an estimation obtained by a simple model based on a Drude metal. (author). 10 refs, 2 figs

  3. Rich magneto-absorption spectra of AAB-stacked trilayer graphene.

    Science.gov (United States)

    Do, Thi-Nga; Shih, Po-Hsin; Chang, Cheng-Peng; Lin, Chiun-Yan; Lin, Ming-Fa

    2016-06-29

    A generalized tight-binding model is developed to investigate the feature-rich magneto-optical properties of AAB-stacked trilayer graphene. Three intragroup and six intergroup inter-Landau-level (inter-LL) optical excitations largely enrich magneto-absorption peaks. In general, the former are much higher than the latter, depending on the phases and amplitudes of LL wavefunctions. The absorption spectra exhibit single- or twin-peak structures which are determined by quantum modes, LL energy spectra and Fermion distribution. The splitting LLs, with different localization centers (2/6 and 4/6 positions in a unit cell), can generate very distinct absorption spectra. There exist extra single peaks because of LL anti-crossings. AAB, AAA, ABA, and ABC stackings considerably differ from one another in terms of the inter-LL category, frequency, intensity, and structure of absorption peaks. The main characteristics of LL wavefunctions and energy spectra and the Fermi-Dirac function are responsible for the configuration-enriched magneto-optical spectra.

  4. Temperature dependence of absorption spectra of P-type GaP

    International Nuclear Information System (INIS)

    Mounir, M.; Balloomal, L.S.

    1985-10-01

    The theoretical analysis of the optical absorption due to band-impurity (impurity-band) electron transitions involving deep impurity levels in semi-conductors is considered. Also the data of the experimental absorption spectra of GaP were performed at room temperature and the results were found to be in agreement with the theoretical results if the electron-phonon interaction is taken into consideration. (author)

  5. Exciton-related nonlinear optical absorption and refractive index change in GaAs-Ga{sub 1-x}Al{sub x}As double quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Guillermo L. [Fisica Teorica y Aplicada, Escuela de Ingenieria de Antioquia, A.A. 7516 Medellin (Colombia); Instituto de Fisica, Universidad de Antioquia, AA 1226 Medellin (Colombia); Mora-Ramos, Miguel E., E-mail: memora@uaem.mx [Fisica Teorica y Aplicada, Escuela de Ingenieria de Antioquia, A.A. 7516 Medellin (Colombia); Facultad de Ciencias, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, C.P. 62209 Cuernavaca, Morelos (Mexico); Instituto de Fisica, Universidad de Antioquia, AA 1226 Medellin (Colombia); Duque, Carlos A. [Instituto de Fisica, Universidad de Antioquia, AA 1226 Medellin (Colombia)

    2013-01-15

    In this work the variations of the exciton-related optical absorption and the change of the refractive index in a GaAs-(Ga,Al)As double quantum well as functions of the geometric parameters of the heterostructure are investigated. The variational method is applied within the framework of the parabolic band and effective mass approximations, in order to obtain the 1s-like exciton energy spectrum. The outcome for the related optical coefficients shows a quenched and redshifted light absorption as a result of the increment in the inner barrier and right-hand well widths, with the possibility of an enhancement of the excitonic contribution to the relative change in the refractive index.

  6. The silicon neighborhood across the a-Si:H to {mu}c-Si transition by X-ray absorption spectroscopy (XAS)

    Energy Technology Data Exchange (ETDEWEB)

    Tessler, Leandro R.; Wang Qi; Branz, Howard M

    2003-04-22

    We report a synchrotron X-ray absorption spectroscopy study of the average neighborhood of Si near the transition from a-Si:H to {mu}c-Si on wedge-shaped samples prepared by hot-wire CVD in a chamber using a movable shutter. The thickness of the wedge varies from 30 to 160 nm. Nucleation of {mu}c-Si occurs at a critical thickness of approximately 100 nm. X-Ray absorption was measured at the Si K-edge (1.84 keV) by total electron photoemission yield. The absorption oscillations in the EXAFS region are very similar to all along the wedge. Analysis indicates an average tetrahedral first neighbor shell with radial disorder decreasing with crystallization. In the near-edge (XANES) region multiple scattering effects appear at the onset of crystallinity. Unlike single crystal silicon, these effects involve only double scattering within the first neighbor shell, indicating an ill-formed second shell in {mu}c-Si.

  7. Mineralogical characterization of arsenic, iron, and nickel in uranium mine tailings using XAS and EMPA

    International Nuclear Information System (INIS)

    Essilfie-Dughan, J.; Hendry, M.J.; Warner, J.; Kotzer, T.

    2010-01-01

    In northern Saskatchewan, Canada, high-grade uranium ores and the resulting tailings can contain high levels of arsenic (As), iron (Fe), and nickel (Ni). An environmental concern in the uranium mining industry is the long-term stabilization of these elements of concern (EOCs) within tailings management facilities thereby mitigating their transfer to the surrounding groundwater. Characterization of these As-, Fe- and Ni-bearing minerals and complexes must be carried out to evaluate their solubility and long-term stability within the tailings mass. Synchrotron-based bulk x-ray absorption spectroscopy (XAS) has been used to study the speciation of these EOCs in mine tailing samples obtained from the Deilmann Tailings Management Facility (DTMF) at Key Lake, Saskatchewan. Electron microprobe analysis (EMPA) and synchrotron-based micro-focussing x-ray fluorescence mapping and absorption spectroscopy (μXRF; μXAS ) have also been employed to study spatial distribution and speciation at the micron scale. Comparisons of K-edge absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As, Fe, and Ni in the mine tailings samples are +5, +3, and +2, respectively, largely reflecting their deposition in an oxidized environment and complexation within stable oxic phases. Backscattered electron (BSE) images of the tailings from the electron microprobe indicate the presence of gypsum/lime nodules surrounded by metallic rims mainly consisting of As, Fe, and Ni. μXRF elemental mapping confirms these EPMA results. μXAS collected within the metal-bearing rims indicates As and Fe is present mainly in the +5 and +3 oxidation state, respectively. (author)

  8. Absorption spectra for collinear (nonreactive) H3: Comparison between quantal and classical calculations

    International Nuclear Information System (INIS)

    Engel, V.; Bacic, Z.; Schinke, R.; Shapiro, M.

    1985-01-01

    Absorption spectra for the collinear (nonreactive) H+H 2 →H/sup number-sign/ 3 →H+H 2 are calculated quantum mechanically, using the Siegbahn--Liu--Truhlar--Horowitz (SLTH) ab initio potential and a model H( 3 surface as the ground and excited H 3 surface, respectively. They are compared to classical spectra previously computed by Mayne, Poirier, and Polanyi using the same potential energy surfaces [J. Chem. Phys. 80, 4025 (1984)]. The spectra are calculated at several collision energies and for both H+H 2 (v = 0) and H+H 2 (v = 1). The quantal and classical spectra are shown to agree with respect to basic features and trends. Nevertheless, the two sets of spectra differ considerably in their overall appearance because of some purely quantum aspects of the H+H 2 system

  9. Protonation effects on the UV/Vis absorption spectra of imatinib: a theoretical and experimental study.

    Science.gov (United States)

    Grante, Ilze; Actins, Andris; Orola, Liana

    2014-08-14

    An experimental and theoretical investigation of protonation effects on the UV/Vis absorption spectra of imatinib showed systematic changes of absorption depending on the pH, and a new absorption band appeared below pH 2. These changes in the UV/Vis absorption spectra were interpreted using quantum chemical calculations. The geometry of various imatinib cations in the gas phase and in ethanol solution was optimized with the DFT/B3LYP method. The resultant geometries were compared to the experimentally determined crystal structures of imatinib salts. The semi-empirical ZINDO-CI method was employed to calculate the absorption lines and electronic transitions. Our study suggests that the formation of the extra near-UV absorption band resulted from an increase of imatinib trication concentration in the solution, while the rapid increase of the first absorption maximum could be attributed to both the formation of imatinib trication and tetracation. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Real-Time Observation of Platinum Redispersion on Ceria-Based Oxide by In-situ Turbo-XAS in Fluorescence Mode

    International Nuclear Information System (INIS)

    Nagai, Yasutaka; Dohmae, Kazuhiko; Tanabe, Toshitaka; Shinjoh, Hirofumi; Takagi, Nobuyuki; Ikeda, Yasuo; Guilera, Gemma; Pascarelli, Sakura; Newton, Mark; Matsumoto, Shin'ichi

    2007-01-01

    A real-time observation of the redispersion behavior of sintered Pt on ceria-based oxide was made possible by in-situ time-resolved Turbo-XAS in fluorescence mode. 2 wt% Pt/Ce-Zr-Y mixed oxide samples were prepared, and then treated under an aging condition. The average Pt particle size measured by CO absorption method after aging was 7 nm. Redispersion treatments of the previously aged catalyst were carried out at 600 deg. C within an in-situ XAS cell in a cyclical flow of reducing/oxidizing gases. Pt L3-edge XANES spectra were collected every 1.1 second under in-situ conditions. From a change in the XANES spectra, we observed that the Pt particle size of the aged catalyst decreased from 7 to 5 nm after 60 seconds and then to 3 nm after 1000 seconds

  11. Oxygen K-edge absorption spectra of small molecules in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O/sub 2/, CO, CO/sub 2/ and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs.

  12. Oxygen K-edge absorption spectra of small molecules in the gas phase

    International Nuclear Information System (INIS)

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O 2 , CO, CO 2 and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs

  13. Optical absorption and magnetic circular dichroism spectra of thiouracils: a quantum mechanical study in solution

    DEFF Research Database (Denmark)

    Martínez-Fernández, L.; Fahleson, Tobias; Norman, Patrick

    2017-01-01

    The excited electronic states of 2-thiouracil, 4-thiouracil and 2,4-dithiouracil, the analogues of uracil where the carbonyl oxygens are substituted by sulphur atoms, have been investigated by computing the magnetic circular dichroism (MCD) and one-photon absorption (OPA) spectra at the time-depe...

  14. Multi-Photon Absorption Spectra: A Comparison Between Transmittance Change and Fluorescence Methods

    Science.gov (United States)

    2015-05-21

    AFRL-OSR-VA-TR-2015-0134 multi-photon absorption spectra Cleber Mendonca INSTITUTO DE FISICA DE SAO CARLOS Final Report 05/21/2015 DISTRIBUTION A...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Instituto de Fisica de Sao Carlos - Universidade de Sao Paulo Av

  15. Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

    Science.gov (United States)

    Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

    2004-01-01

    A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

  16. Core-hole effects in the x-ray-absorption spectra of transition-metal silicides

    NARCIS (Netherlands)

    WEIJS, PJW; CZYZYK, MT; VANACKER, JF; SPEIER, W; GOEDKOOP, JB; VANLEUKEN, H; HENDRIX, HJM; DEGROOT, RA; VANDERLAAN, G; BUSCHOW, KHJ; WIECH, G; FUGGLE, JC

    1990-01-01

    We report systematic differences between the shape of the Si K x-ray-absorption spectra of transition-metal silicides and broadened partial densities of Si p states. We use a variety of calculations to show that the origin of these discrepancies is the core-hole potential appropriate to the final

  17. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Science.gov (United States)

    2010-07-01

    ... applied to measure the absorption spectra. (b) Method—(1)(i) Introduction, purpose, scope, relevance... volume of HCl or NaOH in aqueous solution ([HCl], [NaOH]=1 mol/L). (4) In theory, all chemical species...) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical Rubber...

  18. Quantum theory and experimental studies of absorption spectra and photoisomerization of azobenzene polymers

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Ramanujam, P.S.; Johansen, P.M.

    1998-01-01

    The microscopic properties of azobenzene chromophores are important for a correct description of optical storage systems based on photoinduced anisotropy in azobenzene polymers. A quantum model of these properties is presented and verified by comparison to experimental absorption spectra for trans...

  19. Understanding the features in the ultrafast transient absorption spectra of CdSe quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Cheng; Do, Thanh Nhut [Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Ong, Xuanwei [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Chan, Yinthai [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Institute of Materials Research & Engineering, A*STAR, 2 Fusionopolis Way, Innovis, Singapore 138634 (Singapore); Tan, Howe-Siang, E-mail: howesiang@ntu.edu.sg [Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore)

    2016-12-20

    We describe a model to explain the features of the ultrafast transient absorption (TA) spectra of CdSe core type quantum dots (QDs). The measured TA spectrum consists of contributions by the ground state bleach (GSB), stimulated emission (SE) and excited state absorption (ESA) processes associated with the three lowest energy transition of the QDs. We model the shapes of the GSB, SE and ESA spectral components after fits to the linear absorption. The spectral positions of the ESA components take into account the biexcitonic binding energy. In order to obtain the correct weightage of the GSB, SE and ESA components to the TA spectrum, we enumerate the set of coherence transfer pathways associated with these processes. From our fits of the experimental TA spectra of 65 Å diameter QDs, biexcitonic binding energies for the three lowest energy transitions are obtained.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  2. Studies of the X-ray absorption spectra of some methylcyano esters

    International Nuclear Information System (INIS)

    Takahashi, Osamu; Saito, Ko; Mitani, Masaki; Yoshida, Hiroaki; Tahara, Fumitaka; Sunami, Tetsuji; Waki, Keiichiro; Senba, Yasunori; Hiraya, Atsunari; Pettersson, Lars G.M.

    2005-01-01

    Density functional theory (DFT) has been applied to simulate core-excited photoabsorption spectra for some methylcyano esters within a transition potential (TP) framework. Our calculations for methylcyano formate at the N and O K-edges are consistent with previous experimental spectra. For methylcyano acetate the photoabsorption spectra at the N and O K-edges were reinvestigated experimentally. Contrary to the previous experiment, only one main peak was observed at the N K-edge and this peak was assigned to N(1s) ->π* excitation. This result was supported by our theoretical calculations. The general trends in the X-ray absorption spectra and the site-specific bond scission of methylcyano esters at the N and O K-edges are also discussed

  3. Picosecond transient absorption spectra of aminosalicylates in confirmation of the triple excitation mechanism

    International Nuclear Information System (INIS)

    Gormin, D.

    1989-01-01

    Using picosecond transient absorption studies, it is shown that the twisted intramolecular charge-transfer state (TICT) and the excited intramolecular proton-transfer state (ESIPT or PT) of specific aminosalicylates both contribute to the long-wavelength fluorescence band, F 2 , observed as an unresolved band to the red of the normal fluorescence band, F 1 . The transient absorption band for 2-hydroxy-4-(dimethylamino)benzoic acid methyl ester (PDASE) is shown to be a composite of the two excited-state absorption modes: S n double-prime(TICT) left-arrow S 1 double-prime (TICT) and S n '(PT)left-arrow S 1 '(PT). This corroborates previous steady-state fluorescence studies of the unresolved F 2 band. The assignments are based on comparison with the excited-state absorption spectra of various substituted aminosalicylates in polar and nonpolar solvents

  4. Simulations of absorption spectra of conjugated oligomers: role of planar conformation and aggregation in condensed phase

    Science.gov (United States)

    Yuan, Xiang-Ai; Wen, Jin; Zheng, Dong; Ma, Jing

    2018-04-01

    This Review highlights the structure/property relationship underlying the morphology modulation through various factors towards the exploration of light-absorbing materials for efficient utilisation of solar power. Theoretical study using a combination of molecular dynamics imulations and the time-dependent density functional theory demonstrated that the planarity plays an important role in tuning spectral properties of oligomer aggregates. The aggregation-induced blue-shift in absorption spectra of oligothiophenes and the red-shift for oligofluorenols were rationalised in a unified way from the reduced (and increased) content of planar conformations in molecular aggregates. The planarity versus non-planarity of oligomers can be modulated by introduction of alkyl side chain or steric bulky substituents. The substitution with various groups in the ortho-position of azobenzene leads to the distorted backbone, breaking symmetry, and hence the red-shift in spectra, expanding the application in biological systems with visible light absorption. The donor-acceptor substituent groups in conjugated oligomers can increase the degree of planarity, electron delocalisation and polarisation, and charge separation, giving rise to the red-shift in spectra and enhancement in polarisability and charge mobility for device applications. The solvent dependent and pH-sensitive properties and intramolecular hydrogen bonds also caused the shift of absorption spectra with the appearance of planar conformers.

  5. Temperature dependent absorption spectra of Br(-), Br2(•-), and Br3(-) in aqueous solutions.

    Science.gov (United States)

    Lin, Mingzhang; Archirel, Pierre; Van-Oanh, Nguyen Thi; Muroya, Yusa; Fu, Haiying; Yan, Yu; Nagaishi, Ryuji; Kumagai, Yuta; Katsumura, Yosuke; Mostafavi, Mehran

    2011-05-05

    The absorption spectra of Br(2)(•-) and Br(3)(-) in aqueous solutions are investigated by pulse radiolysis techniques from room temperature to 380 and 350 °C, respectively. Br(2)(•-) can be observed even in supercritical conditions, showing that this species could be used as a probe in pulse radiolysis at high temperature and even under supercritical conditions. The weak temperature effect on the absorption spectra of Br(2)(•-) and Br(3)(-) is because, in these two systems, the transition occurs between two valence states; for example, for Br(2)(-) we have (2)Σ(u) → (2)Σ(g) transition. These valence transitions involve no diffuse final state. However, the absorption band of Br(-) undergoes an important red shift to longer wavelengths. We performed classical dynamics of hydrated Br(-) system at 20 and 300 °C under pressure of 25 MPa. The radial distribution functions (rdf's) show that the strong temperature increase (from 20 to 300 °C) does not change the radius of the solvent first shell. On the other hand, it shifts dramatically (by 1 Å) the second maximum of the Br-O rdf and introduces much disorder. This shows that the first water shell is strongly bound to the anion whatever the temperature. The first two water shells form a cavity of a roughly spherical shape around the anion. By TDDFT method, we calculated the absorption spectra of hydrated Br(-) at two temperatures and we compared the results with the experimental data.

  6. 2D-PES/XAS method for atomic-layer-resolved magnetic structure analysis

    International Nuclear Information System (INIS)

    Matsui, F.; Daimon, H.; Matsushita, T.; Guo, F.Z.

    2008-01-01

    Photoelectron and Auger electron angular distributions from a localized core level provide information on atomic configurations. Forward-focusing peaks indicate the directions of atoms surrounding the excited atom. X-ray absorption fine structure and X-ray magnetic circular dichroism measurements by Auger electron yield detection on the other hand are excellent methods for studying of the electronic and magnetic structures of surfaces, adsorbates, and thin films. However, all the information from atoms within the electron mean-free-path region is averaged into the obtained spectra. Here, we introduce a new method of X-ray absorption spectroscopy (XAS) combined with measurements of Auger electron angular distribution using a display-type analyzer. Taking advantage of the forward-focusing peak as an excellent element- and site-selective probe, 2D-XAS enables direct access to the individual electronic and magnetic structures of each atomic layer. This method was applied to studying the electronic and magnetic structures of Ni thin film at atomic level. (author)

  7. HIGHER ORDER SPECIATION EFFECTS ON PLUTONIUM L3 X-RAY ABSORPTION NEAR EDGE SPECTRA.

    Energy Technology Data Exchange (ETDEWEB)

    Conradson, Steven D.; Abney, Kent D.; Begg, Bruce D.; Brady, Erik D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Lupinetti, Anthony J.; Neu, Mary P.; Palmer, Phillip D.; Paviet-Hartmann, Patricia; Reilly, Sean D.; Runde, Wolfgang H.; Tait, C. Drew; Veirs, D. Kirk

    2003-06-09

    Pu L{sub 3} X-ray Near Edge Absorption Spectra for Pu(0-VII) are reported for more than 50 chalcogenides, chlorides, hydrates, hydroxides, nitrates, carbonates, oxy-hydroxides, and other compounds both as solids and in solution, and substituted in zirconlite, perovksite, and borosilicate glass. This large data base extends the known correlations between the energy and shape of these spectra from the usual association of the XANES with valence and site symmetry to higher order chemical effects. Because of the large number of compounds of these different types a number of novel and unexpected behaviors are observed.

  8. Pulse radiolysis of LiBr-KBr melts. Optical transient absorption spectra

    International Nuclear Information System (INIS)

    Sawamura, S.; Gebicki, J.L.; Mayer, J.; Kroh, J.

    1990-01-01

    Absorption spectra of the irradiated melts of LiBr and LiBr-KBr mixtures were investigated in the temperature range 673-873 K by nanosecond pulse radiolysis. The visible band ascribed to e s - shows the apparent shift towards longer wavelengths with increasing temperature and increasing content of KBr in the mixture. The UV transient absorption was attributed to superimposed Br 2 - and Br 3 - bands. The relation between the transition energy of visible band and the inverse mean ion distance is given for alkali bromide and chloride systems. (author)

  9. XAS Investigations of PEM Fuel Cells

    Science.gov (United States)

    Roth, Christina; Ramaker, David E.

    Polymer-electrolyte membrane (PEM) fuel cells are still far from an area-wide market launch due in part to long-term stability, reliability and cost issues. A more detailed knowledge of the underlying reaction mechanisms is expected to further their application, as it would allow for the design of tailor-made catalysts. However, this will only be possible by complementing traditional in situ studies on single-crystals in electrochemical cells with more sophisticated metal/electrolyte interfacial studies by novel spectroscopic methodologies, which can provide complementary insights into the behaviour of commercial catalysts under real fuel cell operating conditions. This review will focus on the advances of Xray absorption spectroscopy (XAS) in applied fuel cell research utilizing several examples. XAS enables both the nanoparticle morphology and the adsorbate coverage and binding site to be investigated with just one technique. The latter is possible when complementing the conventional extended X-ray absorption fine structure (EXAFS) analysis with the more novel Δμ XANES approach.

  10. Interlayer interactions in absorption and reflection spectra of bismuth HTSC crystals

    International Nuclear Information System (INIS)

    Kruchinin, S.P.; Yaremko, A.M.

    1992-01-01

    The HTSC reflection and absorption optic spectra peculiarities are analysed in the paper on the basis of bismuth and thallium. The approach suggested takes into account the complex character of crystals structure, possible localization of excitations in the isolated layers and further excitations exchange due to the interlayer interaction between cuprate (Cu O) and quasi-degenerate bismuth layers (Bi O/3pO). The expressions for the excitation and intensity energies of the corresponding transitions are obtained. It is shown that only part of excitations whose number is determined by the number of layers in the unit cell will be manifest in optical reflection and absorption spectra. The experimental results on spectral dependence of crystal reflection coefficients are analysed

  11. Comparative study of the hydrostatic pressure and temperature effects on the impurity-related optical properties in single and double GaAs-Ga{sub 1-x}Al{sub x}As quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Odhiambo Oyoko, H. [Department of Physics, Westville Campus, University of KwaZulu-Natal, Private Bag X 54001, Durban 4000 (South Africa); Porras-Montenegro, N. [Departamento de Fisica, Universidad del Valle, AA 25360, Cali (Colombia); Lopez, S.Y. [Facultad de Educacion, Universidad de Antioquia, AA 1226, Medellin (Colombia); Duque, C.A. [Instituto de Fisica, Universidad de Antioquia, AA 1226, Medellin (Colombia)

    2007-07-01

    Using a variational technique within the effective mass approximation we have carried out a comparative study of the effect of hydrostatic pressure and temperature on the shallow-impurity related optical absorption spectra in GaAs-Ga{sub 1-x}Al{sub x}As single and double quantum wells. The results show a pressure dependent read-shift and a temperature dependent blue-shift in the optical absorption spectra. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Dose and absorption spectra response of EBT2 Gafchromic film to high energy X-rays

    International Nuclear Information System (INIS)

    Butson, M.J.; Cheung, T.; Yu, P.K.N.; Alnawaf, H.

    2009-01-01

    Full text: With new advancements in radiochromic film designs and sensitivity to suit different niche applications, EBT2 is the latest offering for the megavoltage radiotherapy market. New construction specifications including different physical construction and the use of a yellow coloured dye has provided the next generation radiochromic film for therapy applications. The film utilises the same active chemical for radiation measurement as its predecessor, EBT Gafchromic. Measurements have been performed using photo spectrometers to analyse the absorption spectra properties of this new EBT2 Gafchromic, radiochromic film. Results have shown that whilst the physical coloration or absorption spectra of the film, which turns yellow to green as compared to EBT film, (clear to blue) is significantly different due to the added yellow dye, the net change in absorption spectra properties for EBT2 are similar to the original EBT film. Absorption peaks are still located at 636 n m and 585 n m positions. A net optical density change of 0.590 ± 0.020 (2SD) for a 1 Gy radiation absorbed dose using 6 MV x-rays when measured at the 636 n m absorption peak was found. This is compared to 0.602 ± 0.025 (2SD) for the original EBT film (2005 Batch) and 0.557 ± 0.027 (2009 Batch) at the same absorption peak. The yellow dye and the new coating material produce a significantly different visible absorption spectra results for the EBT2 film compared to EBT at wavelengths especially below approximately 550 n m. At wavelengths above 550 n m differences in absolute OD are seen however, when dose analysis is performed at wavelengths above 550 n m using net optical density changes, no significant variations are seen. If comparing results of the late production EBT to new production EBT2 film, net optical density variations of approximately 10 % to 15 % are seen. As all new film batches should be calibrated for sensitivity upon arrival this should not be of concern.

  13. Trident: A Universal Tool for Generating Synthetic Absorption Spectra from Astrophysical Simulations

    Science.gov (United States)

    Hummels, Cameron B.; Smith, Britton D.; Silvia, Devin W.

    2017-09-01

    Hydrodynamical simulations are increasingly able to accurately model physical systems on stellar, galactic, and cosmological scales; however, the utility of these simulations is often limited by our ability to directly compare them with the data sets produced by observers: spectra, photometry, etc. To address this problem, we have created trident, a Python-based open-source tool for post-processing hydrodynamical simulations to produce synthetic absorption spectra and related data. trident can (I) create absorption-line spectra for any trajectory through a simulated data set mimicking both background quasar and down-the-barrel configurations; (II) reproduce the spectral characteristics of common instruments like the Cosmic Origins Spectrograph; (III) operate across the ultraviolet, optical, and infrared using customizable absorption-line lists; (IV) trace simulated physical structures directly to spectral features; (v) approximate the presence of ion species absent from the simulation outputs; (VI) generate column density maps for any ion; and (vii) provide support for all major astrophysical hydrodynamical codes. trident was originally developed to aid in the interpretation of observations of the circumgalactic medium and intergalactic medium, but it remains a general tool applicable in other contexts.

  14. Trident: A Universal Tool for Generating Synthetic Absorption Spectra from Astrophysical Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Hummels, Cameron B. [TAPIR, California Institute of Technology, Pasadena, CA 91125 (United States); Smith, Britton D. [San Diego Supercomputer Center, University of California, San Diego, CA 92121 (United States); Silvia, Devin W. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

    2017-09-20

    Hydrodynamical simulations are increasingly able to accurately model physical systems on stellar, galactic, and cosmological scales; however, the utility of these simulations is often limited by our ability to directly compare them with the data sets produced by observers: spectra, photometry, etc. To address this problem, we have created trident, a Python-based open-source tool for post-processing hydrodynamical simulations to produce synthetic absorption spectra and related data. trident can (i) create absorption-line spectra for any trajectory through a simulated data set mimicking both background quasar and down-the-barrel configurations; (ii) reproduce the spectral characteristics of common instruments like the Cosmic Origins Spectrograph; (iii) operate across the ultraviolet, optical, and infrared using customizable absorption-line lists; (iv) trace simulated physical structures directly to spectral features; (v) approximate the presence of ion species absent from the simulation outputs; (vi) generate column density maps for any ion; and (vii) provide support for all major astrophysical hydrodynamical codes. trident was originally developed to aid in the interpretation of observations of the circumgalactic medium and intergalactic medium, but it remains a general tool applicable in other contexts.

  15. Trident: A Universal Tool for Generating Synthetic Absorption Spectra from Astrophysical Simulations

    International Nuclear Information System (INIS)

    Hummels, Cameron B.; Smith, Britton D.; Silvia, Devin W.

    2017-01-01

    Hydrodynamical simulations are increasingly able to accurately model physical systems on stellar, galactic, and cosmological scales; however, the utility of these simulations is often limited by our ability to directly compare them with the data sets produced by observers: spectra, photometry, etc. To address this problem, we have created trident, a Python-based open-source tool for post-processing hydrodynamical simulations to produce synthetic absorption spectra and related data. trident can (i) create absorption-line spectra for any trajectory through a simulated data set mimicking both background quasar and down-the-barrel configurations; (ii) reproduce the spectral characteristics of common instruments like the Cosmic Origins Spectrograph; (iii) operate across the ultraviolet, optical, and infrared using customizable absorption-line lists; (iv) trace simulated physical structures directly to spectral features; (v) approximate the presence of ion species absent from the simulation outputs; (vi) generate column density maps for any ion; and (vii) provide support for all major astrophysical hydrodynamical codes. trident was originally developed to aid in the interpretation of observations of the circumgalactic medium and intergalactic medium, but it remains a general tool applicable in other contexts.

  16. Power-law to Power-law Mapping of Blazar Spectra from Intergalactic Absorption

    International Nuclear Information System (INIS)

    Stecker, F W; Scully, S T

    2007-01-01

    We have derived a useful analytic approximation for determining the effect of intergalactic absorption on the γ-ray spectra of TeV blazars the energy range 0.2 TeV γ γ ) is approximately logarithmic. The effect of this energy dependence is to steepen intrinsic source spectra such that a source with an approximate power-law spectral index Γ s is converted to one with an observed spectral index Γ o ≅ Γ s + ΔΓ(z) where ΔΓ(z) is a linear function of z in the redshift range 0.05-0.4. We apply this approximation to the spectra of 7 TeV blazars

  17. In vivo determination of the absorption and scattering spectra of the human prostate during photodynamic therapy

    Science.gov (United States)

    Finlay, Jarod C.; Zhu, Timothy C.; Dimofte, Andreea; Stripp, Diana C. H.; Malkowicz, S. B.; Whittington, Richard; Miles, Jeremy; Glatstein, Eli; Hahn, Stephen M.

    2004-06-01

    A continuing challenge in photodynamic therapy is the accurate in vivo determination of the optical properties of the tissue being treated. We have developed a method for characterizing the absorption and scattering spectra of prostate tissue undergoing PDT treatment. Our current prostate treatment protocol involves interstitial illumination of the organ via cylindrical diffusing optical fibers (CDFs) inserted into the prostate through clear catheters. We employ one of these catheters to insert an isotropic white light point source into the prostate. An isotropic detection fiber connected to a spectrograph is inserted into a second catheter a known distance away. The detector is moved along the catheter by a computer-controlled step motor, acquiring diffuse light spectra at 2 mm intervals along its path. We model the fluence rate as a function of wavelength and distance along the detector"s path using an infinite medium diffusion theory model whose free parameters are the absorption coefficient μa at each wavelength and two variables A and b which characterize the reduced scattering spectrum of the form μ"s = Aλ-b. We analyze our spectroscopic data using a nonlinear fitting algorithm to determine A, b, and μa at each wavelength independently; no prior knowledge of the absorption spectrum or of the sample"s constituent absorbers is required. We have tested this method in tissue simulating phantoms composed of intralipid and the photosensitizer motexafin lutetium (MLu). The MLu absorption spectrum recovered from the phantoms agrees with that measured in clear solution, and μa at the MLu absorption peak varies linearly with concentration. The ´"s spectrum reported by the fit is in agreement with the known scattering coefficient of intralipid. We have applied this algorithm to spectroscopic data from human patients sensitized with MLu (2 mg kg-1) acquired before and after PDT. Before PDT, the absorption spectra we measure include the characteristic MLu absorption

  18. Determining CDOM Absorption Spectra in Diverse Aquatic Environments Using a Multiple Pathlength, Liquid Core Waveguide System

    Science.gov (United States)

    Miller, Richard L.; Belz, Mathias; DelCastillo, Carlos; Trzaska, Rick

    2001-01-01

    We evaluated the accuracy, sensitivity and precision of a multiple pathlength, liquid core waveguide (MPLCW) system for measuring colored dissolved organic matter (CDOM) absorption in the UV-visible spectral range (370-700 nm). The MPLCW has four optical paths (2.0, 9.8, 49.3, and 204 cm) coupled to a single Teflon AF sample cell. Water samples were obtained from inland, coastal and ocean waters ranging in salinity from 0 to 36 PSU. Reference solutions for the MPLCW were made having a refractive index of the sample. CDOM absorption coefficients, aCDOM, and the slope of the log-linearized absorption spectra, S, were compared with values obtained using a dual-beam spectrophotometer. Absorption of phenol red secondary standards measured by the MPLCW at 558 nm were highly correlated with spectrophotometer values and showed a linear response across all four pathlengths. Values of aCDOM measured using the MPLCW were virtually identical to spectrophotometer values over a wide range of concentrations. The dynamic range of aCDOM for MPLCW measurements was 0.002 - 231.5 m-1. At low CDOM concentrations spectrophotometric aCDOM were slightly greater than MPLCW values and showed larger fluctuations at longer wavelengths due to limitations in instrument precision. In contrast, MPLCW spectra followed an exponential to 600 nm for all samples.

  19. Ultraviolet absorption spectra and kinetics of CH3S and CH2SH radicals

    DEFF Research Database (Denmark)

    Anastasi, C.; Broomfield, M.; Nielsen, O.J.

    1991-01-01

    The ultraviolet absorption spectra of CH3S and CH2SH radicals have been measured between 215 and 380 nm using the pulse-radiolysis/kinetic-absorption method. One absorption band between 250 and 300 nm and one around 215 nm have been tentatively assigned to the CH2SH and CH3S radicals, respectively....... This spectrum has been used to measure the self-reaction rates of these radicals. Rate constants of 4 x 10(-11) and 7 x 10(-11) cm3 molecule-1 s-1 have been measured at 298 K for CH3S and CH2SH recombination, respectively. The possible reaction pathways are discussed....

  20. Quantitative photoacoustic microscopy of optical absorption coefficients from acoustic spectra in the optical diffusive regime.

    Science.gov (United States)

    Guo, Zijian; Favazza, Christopher; Garcia-Uribe, Alejandro; Wang, Lihong V

    2012-06-01

    Photoacoustic (PA) microscopy (PAM) can image optical absorption contrast with ultrasonic spatial resolution in the optical diffusive regime. Conventionally, accurate quantification in PAM requires knowledge of the optical fluence attenuation, acoustic pressure attenuation, and detection bandwidth. We circumvent this requirement by quantifying the optical absorption coefficients from the acoustic spectra of PA signals acquired at multiple optical wavelengths. With the acoustic spectral method, the absorption coefficients of an oxygenated bovine blood phantom at 560, 565, 570, and 575 nm were quantified with errors of <3%. We also quantified the total hemoglobin concentration and hemoglobin oxygen saturation in a live mouse. Compared with the conventional amplitude method, the acoustic spectral method provides greater quantification accuracy in the optical diffusive regime. The limitations of the acoustic spectral method was also discussed.

  1. Depth-selective X-ray absorption spectroscopy by detection of energy-loss Auger electrons

    Energy Technology Data Exchange (ETDEWEB)

    Isomura, Noritake, E-mail: isomura@mosk.tytlabs.co.jp [Toyota Central R& D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192 (Japan); Soejima, Narumasa; Iwasaki, Shiro [Toyota Central R& D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192 (Japan); Nomoto, Toyokazu; Murai, Takaaki [Aichi Synchrotron Radiation Center (AichiSR), 250-3 Minamiyamaguchi-cho, Seto, Aichi 489-0965 (Japan); Kimoto, Yasuji [Toyota Central R& D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192 (Japan)

    2015-11-15

    Graphical abstract: - Highlights: • A unique XAS method is proposed for depth profiling of chemical states. • PEY mode detecting energy-loss electrons enables a variation in the probe depth. • Si K-edge XAS spectra of the Si{sub 3}N{sub 4}/SiO{sub 2}/Si multilayer films have been investigated. • Deeper information was obtained in the spectra measured at larger energy loss. • Probe depth could be changed by the selection of the energy of detected electrons. - Abstract: A unique X-ray absorption spectroscopy (XAS) method is proposed for depth profiling of chemical states in material surfaces. Partial electron yield mode detecting energy-loss Auger electrons, called the inelastic electron yield (IEY) mode, enables a variation in the probe depth. As an example, Si K-edge XAS spectra for a well-defined multilayer sample (Si{sub 3}N{sub 4}/SiO{sub 2}/Si) have been investigated using this method at various kinetic energies. We found that the peaks assigned to the layers from the top layer to the substrate appeared in the spectra in the order of increasing energy loss relative to the Auger electrons. Thus, the probe depth can be changed by the selection of the kinetic energy of the energy loss electrons in IEY-XAS.

  2. Depth-selective X-ray absorption spectroscopy by detection of energy-loss Auger electrons

    International Nuclear Information System (INIS)

    Isomura, Noritake; Soejima, Narumasa; Iwasaki, Shiro; Nomoto, Toyokazu; Murai, Takaaki; Kimoto, Yasuji

    2015-01-01

    Graphical abstract: - Highlights: • A unique XAS method is proposed for depth profiling of chemical states. • PEY mode detecting energy-loss electrons enables a variation in the probe depth. • Si K-edge XAS spectra of the Si_3N_4/SiO_2/Si multilayer films have been investigated. • Deeper information was obtained in the spectra measured at larger energy loss. • Probe depth could be changed by the selection of the energy of detected electrons. - Abstract: A unique X-ray absorption spectroscopy (XAS) method is proposed for depth profiling of chemical states in material surfaces. Partial electron yield mode detecting energy-loss Auger electrons, called the inelastic electron yield (IEY) mode, enables a variation in the probe depth. As an example, Si K-edge XAS spectra for a well-defined multilayer sample (Si_3N_4/SiO_2/Si) have been investigated using this method at various kinetic energies. We found that the peaks assigned to the layers from the top layer to the substrate appeared in the spectra in the order of increasing energy loss relative to the Auger electrons. Thus, the probe depth can be changed by the selection of the kinetic energy of the energy loss electrons in IEY-XAS.

  3. Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

    Science.gov (United States)

    Kokaly, Raymond F.; Skidmore, Andrew K

    2015-01-01

    Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic C-H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the

  4. Retrieval of phytoplankton cell size from chlorophyll a specific absorption and scattering spectra of phytoplankton.

    Science.gov (United States)

    Zhou, Wen; Wang, Guifen; Li, Cai; Xu, Zhantang; Cao, Wenxi; Shen, Fang

    2017-10-20

    Phytoplankton cell size is an important property that affects diverse ecological and biogeochemical processes, and analysis of the absorption and scattering spectra of phytoplankton can provide important information about phytoplankton size. In this study, an inversion method for extracting quantitative phytoplankton cell size data from these spectra was developed. This inversion method requires two inputs: chlorophyll a specific absorption and scattering spectra of phytoplankton. The average equivalent-volume spherical diameter (ESD v ) was calculated as the single size approximation for the log-normal particle size distribution (PSD) of the algal suspension. The performance of this method for retrieving cell size was assessed using the datasets from cultures of 12 phytoplankton species. The estimations of a(λ) and b(λ) for the phytoplankton population using ESD v had mean error values of 5.8%-6.9% and 7.0%-10.6%, respectively, compared to the a(λ) and b(λ) for the phytoplankton populations using the log-normal PSD. The estimated values of C i ESD v were in good agreement with the measurements, with r 2 =0.88 and relative root mean square error (NRMSE)=25.3%, and relatively good performances were also found for the retrieval of ESD v with r 2 =0.78 and NRMSE=23.9%.

  5. Theoretical UV absorption spectra of hydrodynamically escaping O2/CO2-rich exoplanetary atmospheres

    International Nuclear Information System (INIS)

    Gronoff, G.; Mertens, C. J.; Norman, R. B.; Maggiolo, R.; Wedlund, C. Simon; Bell, J.; Bernard, D.; Parkinson, C. J.; Vidal-Madjar, A.

    2014-01-01

    Characterizing Earth- and Venus-like exoplanets' atmospheres to determine if they are habitable and how they are evolving (e.g., equilibrium or strong erosion) is a challenge. For that endeavor, a key element is the retrieval of the exospheric temperature, which is a marker of some of the processes occurring in the lower layers and controls a large part of the atmospheric escape. We describe a method to determine the exospheric temperature of an O 2 - and/or CO 2 -rich transiting exoplanet, and we simulate the respective spectra of such a planet in hydrostatic equilibrium and hydrodynamic escape. The observation of hydrodynamically escaping atmospheres in young planets may help constrain and improve our understanding of the evolution of the solar system's terrestrial planets' atmospheres. We use the dependency of the absorption spectra of the O 2 and CO 2 molecules on the temperature to estimate the temperature independently of the total absorption of the planet. Combining two observables (two parts of the UV spectra that have a different temperature dependency) with the model, we are able to determine the thermospheric density profile and temperature. If the slope of the density profile is inconsistent with the temperature, then we infer the hydrodynamic escape. We address the question of the possible biases in the application of the method to future observations, and we show that the flare activity should be cautiously monitored to avoid large biases.

  6. Two-phonon absorption spectra in CuInSe2

    International Nuclear Information System (INIS)

    Sobotta, H.; Neumann, H.; Kissinger, W.; Riede, V.; Kuehn, G.

    1981-01-01

    An attempt was made to measure and to analyse phonon combination mode spectra of CuInSe 2 and in this way to determine the phonon mode frequencies unknown so far. Considering the absorption coefficient spectra, there are to well-pronounced peaks at 405 and 428 cm -1 at room temperature which are shifted to 412 and 433 cm -1 , respectively, at 105 K. Accounting for the fact that the absorption peaks at 405 and 428 cm -1 show the same temperature shift, it seems to be not unreasonable to assume that all the phonon modes participating in these absorption processes are characterized by the same temperature dependence of the mode frequencies. The corresponding mode Grueneisen parameters have been estimated using the thermal expansion coefficients for CuInSe 2 . Values of 1.7 to 2.0 were obtained being nearly of the same magnitude as the values of the high-energy zone-center modes in CuAlS 2 and CuGaS 2 derived from high-pressure Raman scattering studies

  7. Theory of pump–probe ultrafast photoemission and X-ray absorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Fujikawa, Takashi, E-mail: tfujikawa@faculty.chiba-u.jp; Niki, Kaori

    2016-01-15

    Highlights: • Pump–probe ultrafast XAFS and XPS spectra are theoretically studied. • Keldysh Green's function theory is applied. • Important many-body effects are explicitly included. - Abstract: Keldysh Green's function approach is extensively used in order to derive practical formulas to analyze pump–probe ultrafast photoemission and X-ray absorption spectra. Here the pump pulse is strong enough whereas the probe X-ray pulse can be treated by use of a perturbation theory. We expand full Green's function in terms of renormalized Green's function without the interaction between electrons and probe pulse. The present theoretical formulas allow us to handle the intrinsic and extrinsic losses, and furthermore resonant effects in X-ray Absorption Fine Structures (XAFS). To understand the radiation field screening in XPS spectra, we have to use more sophisticated theoretical approach. In the ultrafast XPS and XAFS analyses the intrinsic and extrinsic loss effects can interfere as well. In the XAFS studies careful analyses are necessary to handle extrinsic losses in terms of damped photoelectron propagation. The nonequilibrium dynamics after the pump pulse irradiation is well described by use of the time-dependent Dyson orbitals. Well above the edge threshold, ultrafast photoelectron diffraction and extended X-ray absorption fine structure (EXAFS) provide us with transient structural change after the laser pump excitations. In addition to these slow processes, the rapid oscillation in time plays an important role related to pump electronic excitations. Near threshold detailed information could be obtained for the combined electronic and structural dynamics. In particular high-energy photoemission and EXAFS are not so influenced by the details of excited states by pump pulse. Random-Phase Approximation (RPA)-boson approach is introduced to derive some practical formulas for time-dependent intrinsic amplitudes.

  8. Optical absorption spectra of semiconductors and insulators: ab initio calculation of many-body effects

    International Nuclear Information System (INIS)

    Albrecht, Stefan

    1999-01-01

    A method for the inclusion of self-energy and excitonic effects in first-principle calculations of absorption spectra, within the state-of-the-art plane wave pseudopotential approach, is presented. Starting from a ground state calculation, using density functional theory (DFT) in the local density approximation (LDA), we correct the exchange-correlation potential of DFT-LDA with the self-energy applying Hedin's GW approximation to obtain the physical quasiparticles states. The electron-hole interaction is treated solving an effective two-particle equation, which we derive from Hedin's coupled integral equations, leading to the fundamental Bethe-Salpeter equation in an intermediate step. The interaction kernel contains the screened electron-hole Coulomb interaction and the electron-hole exchange effects, which reflect the microscopic structure of the system and are thus also called local-field effects. We obtain the excitonic eigenstates through diagonalization. This allows us a detailed analysis of the optical properties. The application of symmetry properties enables us to reduce the size of the two-particle Hamiltonian matrix, thus minimizing the computational effort. We apply our method to silicon, diamond, lithium oxide and the sodium tetramer. Good agreement with experiment is obtained for the absorption spectra of Si and diamond, the static dielectric constant of diamond, and for the onset of optical absorption of Li 2 O due to discrete bound excitons. We discuss various approximations of our method and show the strong mixing of independent particle transitions to a bound excitonic state in the Na 4 cluster. The influence of ground state calculations on optical spectra is investigated under particular consideration of the pseudopotential generation and we discuss the use of different Brillouin zone point sampling schemes for spectral calculations. (author) [fr

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

    Energy Technology Data Exchange (ETDEWEB)

    Vorwerk, Christian [Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin, European Theoretical Spectroscopy; Hartmann, Claudia [Renewable Energy, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany; Cocchi, Caterina [Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin, European Theoretical Spectroscopy; Sadoughi, Golnaz [Clarendon Laboratory, Department of Physics, University of Oxford, Oxford OX1 3PU, United Kingdom; Habisreutinger, Severin N. [Clarendon Laboratory, Department of Physics, University of Oxford, Oxford OX1 3PU, United Kingdom; Chemistry and Nanoscience Center, National Renewable Energy Laboratory (NREL), Golden, Colorado, United States; Félix, Roberto [Renewable Energy, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany; Wilks, Regan G. [Renewable Energy, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany; Energy Materials In-Situ Laboratory Berlin (EMIL), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany; Snaith, Henry J. [Clarendon Laboratory, Department of Physics, University of Oxford, Oxford OX1 3PU, United Kingdom; Bär, Marcus [Renewable Energy, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany; Energy Materials In-Situ Laboratory Berlin (EMIL), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany; Draxl, Claudia [Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin, European Theoretical Spectroscopy

    2018-03-23

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L3 and the Pb M5 edges of the methylammonium lead iodide (MAPbI3) hybrid inorganic-organic perovskite and its binary phase PbI2. 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 MAPbI3 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.

  10. Temperature dependence of the optical absorption spectra of InP/ZnS quantum dots

    Science.gov (United States)

    Savchenko, S. S.; Vokhmintsev, A. S.; Weinstein, I. A.

    2017-03-01

    The optical-absorption spectra of InP/ZnS (core/shell) quantum dots have been studied in a broad temperature range of T = 6.5-296 K. Using the second-order derivative spectrophotometry technique, the energies of optical transitions at room temperature were found to be E 1 = 2.60 ± 0.02 eV (for the first peak of excitonic absorption in the InP core) and E 2 = 4.70 ± 0.02 eV (for processes in the ZnS shell). The experimental curve of E 1( T) has been approximated for the first time in the framework of a linear model and in terms of the Fan's formula. It is established that the temperature dependence of E 1 is determined by the interaction of excitons and longitudinal acoustic phonons with hω = 15 meV.

  11. Sharp Absorption Peaks in THz Spectra Valuable for Crystal Quality Evaluation of Middle Molecular Weight Pharmaceuticals

    Science.gov (United States)

    Sasaki, Tetsuo; Sakamoto, Tomoaki; Otsuka, Makoto

    2018-05-01

    Middle molecular weight (MMW) pharmaceuticals (MW 400 4000) are attracting attention for their possible use in new medications. Sharp absorption peaks were observed in MMW pharmaceuticals at low temperatures by measuring with a high-resolution terahertz (THz) spectrometer. As examples, high-resolution THz spectra for amoxicillin trihydrate, atorvastatin calcium trihydrate, probucol, and α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin p-toluenesulfonate (TMPyP) were obtained at 10 K. Typically observed as peaks with full width at half-height (FWHM) values as low as 5.639 GHz at 0.96492 THz in amoxicillin trihydrate and 8.857 GHz at 1.07974 THz for probucol, many sharp peaks of MMW pharmaceuticals could be observed. Such narrow absorption peaks enable evaluation of the crystal quality of MMW pharmaceuticals and afford sensitive detection of impurities.

  12. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    Science.gov (United States)

    2016-06-03

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited -State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited -State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited -state

  13. Combined XRD and XAS

    International Nuclear Information System (INIS)

    Ehrlich, S.N.; Hanson, J.C.; Lopez Camara, A.; Barrio, L.; Estrella, M.; Zhou, G.; Si, R.; Khalid, S.; Wang, Q.

    2011-01-01

    X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) are complementary techniques for investigating the structure of materials. XRD probes long range order and XAFS probes short range order. We have combined the two techniques at one synchrotron beamline, X18A at the NSLS, allowing samples to be studied in a single experiment. This beamline will allow for coordinated measurements of local and long range structural changes in chemical transformations and phase transitions using both techniques.

  14. Modulated microwave absorption spectra from Josephson junctions on a scratched niobium wire

    International Nuclear Information System (INIS)

    Rubins, R.S.; Hutton, S.L.; Ravindran, K.; Subbaraman, K.; Drumheller, J.E.

    1997-01-01

    Modulated microwave absorption (MMA) spectra from Josephson junction formations on a scratched Nb wire have been studied at 9.3 GHz and 4 K. The peak-to-peak separation, δH of the Josephson lines was found to vary linearly with P 1/2 , where P is the applied microwave power, in contrast to a recent interpretation of junction formation in pressed lead pieces by Rubins, Drumheller, and Trybula. The interpretation of the MMA data on Nb are given in terms of the theory of Vichery, Beuneu, and Lejay for superconducting loops containing weak links. copyright 1997 The American Physical Society

  15. Water vapor absorption spectra of the upper atmosphere /45-185 per cm/

    Science.gov (United States)

    Augason, G. C.; Mord, A. J.; Witteborn, F. C.; Erickson, E. F.; Swift, C. D.; Caroff, L. J.; Kunz, L. W.

    1975-01-01

    The far IR nighttime absorption spectrum of the earth's atmosphere above 14 km is determined from observations of the bright moon. The spectra were obtained using a Michelson interferometer attached to a 30-cm telescope aboard a high-altitude jet aircraft. Comparison with a single-layer model atmosphere implies a vertical column of 3.4 plus or minus 0.4 microns of precipitable water on 30 August 1971 and 2.4 plus or minus 0.3 microns of precipitable water on 6 January 1972.-

  16. Absorption Spectra of CuGaSe2 and CuInSe2 Semiconducting Nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2015-10-01

    The structural and optical properties of the chalcopyrite CunGanSe2n and CunInnSe2n nanoclusters (n = 2, 4, 6, and 8) are investigated as a function of the size using a combination of basin-hopping global optimization and time-dependent density functional theory. Although the lowest energy structures are found to show almost random geometries, the band gaps and absorption spectra still are subject to systematic blue shifts for decreasing cluster size in the case of CunGanSe2n, indicating strong electron confinement. The applicability of the nanoclusters in photovoltaics is discussed. © 2015 American Chemical Society.

  17. Alkali-Responsive Absorption Spectra and Third-Order Optical Nonlinearities of Imino Squaramides

    International Nuclear Information System (INIS)

    Li Zhong-Yu; Xu Song; Zhou Xin-Yu; Zhang Fu-Shi

    2012-01-01

    Third-order optical nonlinearities and dynamic responses of two imino squaramides under neutral and base conditions were studied using the femtosecond degenerate four-wave mixing technique at 800 nm. Ultrafast optical responses have been observed and the magnitude of the second-order hyperpolarizabilities of the squaramides has been measured to be as large as 10 −31 esu. The absorption spectra, color of solution, and third-order optical nonlinearities of two imino squaramides change with the addition of sodium hydroxide. The γ value under the base condition for each dye is approximately 1.25 times larger than that under neutral conditions. (fundamental areas of phenomenology(including applications))

  18. Effect of Molar Concentration on Optical Absorption Spectra of ZnS:Mn Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ravi Sharma

    2010-01-01

    Full Text Available The present paper reports the synthesis and characterization of luminescent nanocrystals of manganese doped zinc sulphide. Nanocrystals of zinc sulphide were prepared by chemical precipitation method using the solution of zinc chloride, sodium sulphide, manganese chloride and mercaptoethanol was used as the capping agent. It was found that change in the molar concentration changes the particle size. The particle size of such nanocrystals was measured using XRD pattern and it is found to be in between 3 nm – 5 nm. The blue-shift in absorption spectra was found with reducing size of the nanoparticles

  19. Two-phonon absorption spectra and lattice vibration anisotropy in HfS2

    International Nuclear Information System (INIS)

    Riede, V.; Neumann, H.; Sobotta, H.

    1983-01-01

    The infrared absorption spectra for E-vector perpendicular to c-vector in the two-phonon combination mode range is measured and analysed in order to get additional information about the A/sub 2u/ mode frequencies in HfS 2 . The lattice vibrational properties have been analysed in terms of the polarizable ion model. This model accounts for the long-range Coulomb terms of the charge and the static dipole induced by the structural anisotropy at each anion site

  20. Absorption spectra of thin films of triple compounds in the system RbIPbI2

    International Nuclear Information System (INIS)

    Yunakova, O.N.; Miloslavskij, V.K.; Ksenofontova, E.V.; Kovalenko, E.N.

    2012-01-01

    A formation of compounds RbPbI 3 and Rb 4 PbI 6 in the system RbI-PbI 2 is revealed and their absorption spectra are investigated in an energy interval 2-6 eV and a temperatures range 90-500 K. It is established that the low-frequency exciton excitations are localized in PbI 6 4- structural elements of the crystal lattice, they are classified as excitons of intermediate coupling and are of a three-dimensional character in RbPbI 3 and a quasi-two-dimensional one in Rb 4 PbI 6 .

  1. Temperature-dependent mid-IR absorption spectra of gaseous hydrocarbons

    International Nuclear Information System (INIS)

    Klingbeil, Adam E.; Jeffries, Jay B.; Hanson, Ronald K.

    2007-01-01

    Quantitative mid-IR absorption spectra (2500-3400 cm -1 ) for 12 pure hydrocarbon compounds are measured at temperatures ranging from 25 to 500 deg. C using an FTIR spectrometer. The hydrocarbons studied are n-pentane, n-heptane, n-dodecane, 2,2,4-trimethyl-pentane (iso-octane), 2-methyl-butane, 2-methyl-pentane, 2,4,4-trimethyl-1-pentene, 2-methyl-2-butene, propene, toluene, m-xylene, and ethylbenzene. Room-temperature measurements of neat hydrocarbon vapor were made with an instrument resolution of both 0.1 and 1 cm -1 (FWHM) to confirm that the high-resolution setting was required only to resolve the propene absorption spectrum while the spectra of the other hydrocarbons could be resolved with 1 cm -1 resolution. High-resolution (0.1 cm -1 ), room-temperature measurements of neat hydrocarbons were made at low pressure (∼1 Torr, 133 Pa) and compared to measurements of hydrocarbon/N 2 mixtures at atmospheric pressure to verify that no pressure broadening could be observed over this pressure range. The temperature was varied between 25 and 500 o C for atmospheric-pressure measurements of hydrocarbon/N 2 mixtures (X hydrocarbon ∼0.06-1.5%) and it was found that the absorption cross section shows simple temperature-dependent behavior for a fixed wavelength over this temperature range. Comparisons with previous FTIR data over a limited temperature range and with high-resolution laser absorption data over a wide temperature range show good agreement

  2. The absorption spectra of Pu(VI), -(V) and -(IV) produced electrochemically in carbonate-bicarbonate media

    International Nuclear Information System (INIS)

    Wester, D.W.; Sullivan, J.C.

    1983-01-01

    Absorption spectra in carbonate and bicarbonate media have been measured for various oxidation states of plutonium. The oxidation state of plutonium was adjusted electrochemically (Pu(VI)-V), Esub(f)=+0.11 V vs. SCE) to avoid contamination by redox reagents. In carbonate medium the spectra of Pu(VI) and Pu(V) showed marked differences from the spectra of the same oxidation state in acidic solutions. In bicarbonate the spectra of Pu(VI) and Pu(IV) also differed from the corresponding spectra in acidic media. Reduction to Pu(III) resulted in a precipitate in both carbonate and bicarbonate media. (author)

  3. Identifying Student and Teacher Difficulties in Interpreting Atomic Spectra Using a Quantum Model of Emission and Absorption of Radiation

    Science.gov (United States)

    Savall-Alemany, Francisco; Domènech-Blanco, Josep Lluís; Guisasola, Jenaro; Martínez-Torregrosa, Joaquín

    2016-01-01

    Our study sets out to identify the difficulties that high school students, teachers, and university students encounter when trying to explain atomic spectra. To do so, we identify the key concepts that any quantum model for the emission and absorption of electromagnetic radiation must include to account for the gas spectra and we then design two…

  4. Gas phase UV and IR absorption spectra of CxF2x+1CHO (x=1-4)

    DEFF Research Database (Denmark)

    Hashikawa, Y; Kawasaki, M; Waterland, RL

    2004-01-01

    The UV and IR spectra of CxF2x+1 CHO (x = 1-4) were investigated using computational and experimental techniques. CxF2x+1CHO (x = 1-4) have broad UV absorption features centered at 300-310 nm. The maximum absorption cross-section increases significantly and shifts slightly to the red with increased...

  5. The Associated Absorption Features in Quasar Spectra of the Sloan Digital Sky Survey. I. Mg II Absorption Doublets

    Science.gov (United States)

    Chen, Zhi-Fu; Huang, Wei-Rong; Pang, Ting-Ting; Huang, Hong-Yan; Pan, Da-Sheng; Yao, Min; Nong, Wei-Jing; Lu, Mei-Mei

    2018-03-01

    Using the SDSS spectra of quasars included in the DR7Q or DR12Q catalogs, we search for Mg II λλ2796, 2803 narrow absorption doublets in the spectra data around Mg II λ2798 emission lines. We obtain 17,316 Mg II doublets, within the redshift range of 0.3299 ≤ z abs ≤ 2.5663. We find that a velocity offset of υ r 6000 km s‑1. If associated Mg II absorbers are defined by υ r present at least one associated Mg II system with {W}{{r}}λ 2796≥slant 0.2 \\mathringA . The fraction of associated Mg II systems with high-velocity outflows correlates with the average luminosities of their central quasars, indicating a relationship between outflows and the quasar feedback power. The υ r distribution of the outflow Mg II absorbers is peaked at 1023 km s‑1, which is smaller than the corresponding value of the outflow C IV absorbers. The redshift number density evolution of absorbers (dn/dz) limited by υ r > ‑3000 km s‑1 differs from that of absorbers constrained by υ r > 2000 km s‑1. Absorbers limited by υ r > 2000 km s‑1 and higher values exhibit profiles similar to dn/dz. In addition, the dn/dz is smaller when absorbers are constrained with larger υ r . The distributions of equivalent widths, and the ratio of {W}rλ 2796/{W}rλ 2803, are the same for associated and intervening systems, and independent of quasar luminosity.

  6. VizieR Online Data Catalog: Sgr B2 los molecular absorption line spectra (Corby+, 2018)

    Science.gov (United States)

    Corby, J. F.; McGuire, B. A.; Herbst, E.; Remijan, A. J.

    2017-11-01

    Spectra covering transitions of c-C3H2, c-H1 SO, CCS, H2CS, HCS+, OH, SiO, 29SiO, H2CO, H2(13C)O, l-C3H, and l-C3H+ with line-of-sight absorption observed in the 1-50 GHz data from the PRebiotic Interstellar MOlecular Survey (PRIMOS) taken with the Robert C. Byrd Green Bank Telescope (GBT). Data were observed between 2001 and 2014, with the majority of the data obtained in 2007 in GBT Key Science project ID GBT07A-051. Spectra have been baseline-subtracted using best fit polynomials as described in the paper, and normalized by the continuum, so that the y-axis represents (T/TC-1). Data are provided in the FITS format; each FITS file contains all lines of a single molecule that are observed to have foreground absorption. Please refer to Table 1 of the paper to obtain molecular transition rest frequencies, energies, GBT beam sizes, and transition quantum numbers. (2 data files).

  7. Effect of ladder diagrams on optical absorption spectra in a quasiparticle self-consistent GW framework

    Science.gov (United States)

    Cunningham, Brian; Grüning, Myrta; Azarhoosh, Pooya; Pashov, Dimitar; van Schilfgaarde, Mark

    2018-03-01

    We present an approach to calculate the optical absorption spectra that combines the quasiparticle self-consistent GW method [Phys. Rev. B 76, 165106 (2007), 10.1103/PhysRevB.76.165106] for the electronic structure with the solution of the ladder approximation to the Bethe-Salpeter equation for the macroscopic dielectric function. The solution of the Bethe-Salpeter equation has been implemented within an all-electron framework, using a linear muffin-tin orbital basis set, with the contribution from the nonlocal self-energy to the transition dipole moments (in the optical limit) evaluated explicitly. This approach addresses those systems whose electronic structure is poorly described within the standard perturbative GW approaches with density-functional theory calculations as a starting point. The merits of this approach have been exemplified by calculating optical absorption spectra of a strongly correlated transition metal oxide, NiO, and a narrow gap semiconductor, Ge. In both cases, the calculated spectrum is in good agreement with the experiment. It is also shown that for systems whose electronic structure is well-described within the standard perturbative GW , such as Si, LiF, and h -BN , the performance of the present approach is in general comparable to the standard GW plus Bethe-Salpeter equation. It is argued that both vertex corrections to the electronic screening and the electron-phonon interaction are responsible for the observed systematic overestimation of the fundamental band gap and spectrum onset.

  8. Effect of absorption discontinuity on neutron spectra of water assemblies poisoned with non-1/V absorbers

    International Nuclear Information System (INIS)

    Gupta, I.J.; Trikha, S.K.

    1977-01-01

    Calculations are presented of the diffusion of thermal neutrons (2.5 x 10 -4 to 7 x 10 -1 eV) across an absorption discontinuity in a water assembly, consisting of pure water on one side and aqueous solutions of three different non-1/V absorbers on the other, which were obtained by solving the Boltzmann transport equation in the diffusion approximation using the multigroup formalism. The gradual appearance and disappearance of the depletion region in the neutron spectra (caused by the resonance absorption peaks at energies 0.096 and 0.179 eV for samarium and cadmium respectively), as one moves from the pure water assembly to the poisoned water assembly and vice versa, have also been studied. The minimum concentrations of Sm and Cd atoms in water for which the depletion region in the spectra just starts building up are found to be 60 x 10 18 Sm atom cm -3 and 125 x 10 18 Cd atom cm -3 respectively. However no such depletion region is observed in gadolinium-poisoned water assembly. At the boundary, the equilibrium neutron distribution gets disturbed and is re-established to the equilibrium distribution of the second medium at some distance from the interface. The diffusion lengths so calculated from the total neutron density curves are in good agreement with the experimental results of Goddard and Johnson (Nucl. Sci. Eng.; 37:127 (1969)) at various concentrations of Gd and Cd atoms in water. (author)

  9. Photosynthetic complex LH2 – Absorption and steady state fluorescence spectra

    International Nuclear Information System (INIS)

    Zapletal, David; Heřman, Pavel

    2014-01-01

    Nowadays, much effort is devoted to the study of photosynthesis which could be the basis for an ideal energy source in the future. To be able to create such an energy source – an artificial photosynthetic complex, the first step is a detailed understanding of the function of photosynthetic complexes in living organisms. Photosynthesis starts with the absorption of a solar photon by one of the LH (light-harvesting) pigment–protein complexes and transferring the excitation energy to the reaction center where a charge separation is initiated. The geometric structure of some LH complexes is known in great detail, e.g. for the LH2 complexes of purple bacteria. For understanding of photosynthesis first stage efficiency, it is necessary to study especially optical properties of LH complexes. In this paper we present simulated absorption and steady-state fluorescence spectra for ring molecular system within full Hamiltonian model. Such system can model bacteriochlorophyll ring of peripheral light-harvesting complex LH2 from purple bacterium Rhodopseudomonas acidophila (Rhodoblastus acidophilus). Dynamic disorder (coupling with phonon bath) simultaneously with uncorrelated static disorder (transfer integral fluctuations) is used in our present simulations. We compare and discuss our new results with our previously published ones and of course with experimental data. - Highlights: • We model absorption and steady state fluorescence spectra for B850 ring from LH2. • Fluctuations of environment is modelled by static and dynamic disorder. • Full Hamiltonian model is compared with the nearest neighbour approximation one. • Simulated fluorescence spectrum is compared with experimental data

  10. Plastocyanin conformation: an analysis of its near ultraviolet absorption and circular dichroic spectra

    International Nuclear Information System (INIS)

    Draheim, J.E.; Anderson, G.P.; Duane, J.W.; Gross, E.L.

    1986-01-01

    The near-ultraviolet absorption and circular dichroic spectra of plastocyanin are dependent upon the redox state, solution pH, and ammonium sulfate concentration. This dependency was observed in plastocyanin isolated from spinach, poplar, and lettuce. Removal of the copper atom also perturbed the near-ultraviolet spectra. Upon reduction there are increases in both extinction and ellipticity at 252 nm. Further increases at 252 nm were observed upon formation of apo plastocyanin eliminating charge transfer transitions as the cause. The spectral changes in the near-ultraviolet imply a flexible tertiary conformation for plastocyanin. There are at least two charge transfer transitions at ∼295-340 nm. One of these transitions is sensitive to low pH's and is attributed to the His 87 copper ligand. The redox state dependent changes observed in the near-ultraviolet spectra of plastocyanin are attenuated either by decreasing the pH to 5 or by increasing the ammonium sulfate concentration to 2.7 M. This attenuation cannot be easily explained by simple charge screening. Hydrophobic interactions probably play an important role in this phenomenon. The pH and redox state dependent conformational changes may play an important role in regulating electron transport

  11. Absorption spectra response of XRQA radiochromic film to x-ray radiation

    International Nuclear Information System (INIS)

    Alnawaf, Hani; Cheung, Tsang; Butson, Martin J.; Yu, Peter K.N.

    2010-01-01

    Gafchromic XRQA, radiochromic film is a high sensitivity auto developing x-ray analysis films designed and available for kilovoltage x-ray, dose and QA assessment applications. The film is designed for reflective analysis with a yellow transparent top filter and white opaque backing materials. This allows the film to be visually inspected for colour changes with a higher level of contrast than clear coated radiochromic films such as Gafchromic EBT version 1. The spectral absorption properties in the visible wavelengths have been investigated and results show two main peaks in absorption located at 636 nm and 585 nm. These peaks are located in the same position as EBT Gafchromic film highlighting a similar chemical monomer/polymer for radiation sensitivity. A much higher sensitivity however is found at kilovoltage energies with an average 1.55 OD units per 20 cGy irradiation variation measured at 636 nm using 150 kVp x-rays. This is compared to approximately 0.12 OD units per 20 cGy measured at 636 nm for EBT film at 6 MV x-ray energy. That is, the XRQA film is more than 10 times more sensitive than EBT1 film. The visual colour change is enhanced by the yellow polyester coating. However this does not affect the absorption spectra properties in the red region of analysis which is the main area for use using desktop scanners in reflection mode.

  12. Study of absorption spectra for alkali and alkaline earth metal salts in flameless atomic absorption spectrometry using a carbon tube atomizer

    International Nuclear Information System (INIS)

    Yasuda, Seiji; Kakiyama, Hitoo

    1975-01-01

    Absorption spectra of various salts such as alkali metal salts, alkaline earth dichlorides, and ammonium halides were investigated and absorptions of some molecular species produced in the carbon tube were identified. The aqueous solution (20 μl) containing 1.0 mg/ml of each salt was placed in the carbon tube atomizer and heated in a similar manner to usual flameless atomic absorption method. D 2 -lamp was used as a continuous light source and argon gas was employed as an inert sheath gas. The spectra were obtained over the range of wavelength 200 to 350 nm. When alkali halides were feeded, the absorption spectra agreed with those of alkali halide vapors. Therefore, in such cases vapors of the alkali halides were probably produced by the sublimation or vaporization in the atomizer. The spectra of alkali perchlorates were considered to be those of alkali chlorides produced by the pyrolysis of the perchlorates in the atomizer. The absorptions of alkaline earth chlorides below 250 nm were probably due to their gaseous states. Sulfur dioxide was found to be produced by the pyrolysis of alkali sulfates, bisulfates and sulfites in the atomizer, Alkali phosphates and pyrophosphates gave almost identical spectra below 300 nm. Gamma band spectrum of nitrogen monoxide was observed from 200 to 240 nm during ashing at bout 330 0 C for alkali nitrates and nitrites. Ammonia vapor was produced from ammonium halides during drying at about 170 0 C. Although the absorptions of alkali carbonates and hydroxides were almost undetectable, the same spectra as those of alkali halides were observed by the addition of ammonium halides to the solutions of alkali compounds. This shows that alkali halides are produced in the atomizer by the addition of halide ions. (auth.)

  13. In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method

    International Nuclear Information System (INIS)

    Nagasaka, Masanari; Kosugi, Nobuhiro; Yuzawa, Hayato; Horigome, Toshio

    2014-01-01

    In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates

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

    Science.gov (United States)

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

    2016-12-01

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

  15. Studies on solvatochromic behavior of some monoazo derivatives using electronic absorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Sidir, Isa; Tasal, Erol; Guelseven, Yadigar [Department of Physics, Faculty of Arts and Sciences, Eskisehir Osmangazi University, 26480 Eskisehir (Turkey); Guengoer, Tayyar [Department of Physics, Faculty of Arts and Sciences, Akdeniz University, Antalya (Turkey); Berber, Halil [Department of Chemistry, Faculty of Sciences, Anadolu University, Eskisehir (Turkey); Oegretir, Cemil [Department of Chemistry, Faculty of Arts and Sciences, Eskisehir Osmangazi University, Eskisehir (Turkey)

    2009-06-15

    The electronic absorption spectra of 2',4'-dihydroxy-2-methoxyazobenzene and 4,2',4'-trihydroxyazobenzene molecules have been investigated in solvents with different polarities. The solvent dependent UV-vis spectral shifts, {nu}{sub max}, were analysed using some physical parameters such as refractive index, dielectric constant, Kamlet-Taft parameters, {alpha} (hydrogen bond donating ability) and {beta} (hydrogen bond accepting ability). The electronic transitions are assigned and the solvent induced spectral shifts have been analysed in relation to different solute-solvent interaction mechanisms using linear regression analysis. The results of fitting coefficients obtained from the analysis helped us to estimate the contribution of each type of interaction to the spectral shift in the molecule under consideration. It is concluded that the electronic character of the chemical nature of the solvent and the electronic character of substituents are the important factor for the observed solvatochromism. (author)

  16. kspectrum: an open-source code for high-resolution molecular absorption spectra production

    International Nuclear Information System (INIS)

    Eymet, V.; Coustet, C.; Piaud, B.

    2016-01-01

    We present the kspectrum, scientific code that produces high-resolution synthetic absorption spectra from public molecular transition parameters databases. This code was originally required by the atmospheric and astrophysics communities, and its evolution is now driven by new scientific projects among the user community. Since it was designed without any optimization that would be specific to any particular application field, its use could also be extended to other domains. kspectrum produces spectral data that can subsequently be used either for high-resolution radiative transfer simulations, or for producing statistic spectral model parameters using additional tools. This is a open project that aims at providing an up-to-date tool that takes advantage of modern computational hardware and recent parallelization libraries. It is currently provided by Méso-Star (http://www.meso-star.com) under the CeCILL license, and benefits from regular updates and improvements. (paper)

  17. Comparison of absorption spectra of adenocarcinoma and squamous cell carcinoma cervical tissue

    Science.gov (United States)

    Peresunko, O. P.; Zelinska, N. V.; Prydij, O. G.; Zymnyakov, D. A.; Ushakova, O. V.

    2013-12-01

    We studied a methods of assessment of a connective tissue of cervix in terms of specific volume of fibrous component and an optical density of staining of connective tissue fibers in the stroma of squamous cancer and cervix adenocarcinoma. An absorption spectra of blood plasma of the patients suffering from squamous cancer and cervix adenocarcinoma both before the surgery and in postsurgical periods were obtained. Linear dichroism measurements transmittance in polarized light at different orientations of the polarization plane relative to the direction of the dominant orientation in the structure of the sample of biotissues of stroma of squamous cancer and cervix adenocarcinoma were carried. Results of the investigation of the tumor tissues showed that the magnitude of the linear dichroism Δ is insignificant in the researched spectral range λ=280-840 nm and specific regularities in its change observed short-wave ranges.

  18. Effect of Pressure on Absorption Spectra of Lycopene in n-Hexane and CS2 Solvents

    Science.gov (United States)

    Zhang, Wei; Liu, Wei-Long; Zheng, Zhi-Ren; Huo, Ming-Ming; Li, Ai-Hua; Yang, Bin

    2010-01-01

    The absorption spectra of lycopene in n-hexane and CS2 are measured under high pressure and the results are compared with β-carotene. In the lower pressure range, the deviation from the linear dependence on the Bayliss parameter (BP) for β-carotene is more visible than that for lycopene. With the further increase of the solvent BP, the 0-0 bands of lycopene and β-carotene red shift at almost the same rate in n-hexane; however, the 0-0 band of lycopene red shifts slower than that of β-carotene in CS2. The origins of these diversities are discussed taking into account the dispersion interactions and structures of solute and solvent molecules.

  19. Effect of Pressure on Absorption Spectra of Lycopene in n-Hexane and CS2 Solvents

    International Nuclear Information System (INIS)

    Wei, Zhang; Wei-Long, Liu; Zhi-Ren, Zheng; Ming-Ming, Huo; Ai-Hua, Li; Bin, Yang

    2010-01-01

    The absorption spectra of lycopene in n-hexane and CS 2 are measured under high pressure and the results are compared with β-carotene. In the lower pressure range, the deviation from the linear dependence on the Bayliss parameter (BP) for β-carotene is more visible than that for lycopene. With the further increase of the solvent BP, the 0–0 bands of lycopene and β-carotene red shift at almost the same rate in n-hexane; however, the 0–0 band of lycopene red shifts slower than that of β-carotene in CS 2 . The origins of these diversities are discussed taking into account the dispersion interactions and structures of solute and solvent molecules. (atomic and molecular physics)

  20. VARIABILITY OF WATER AND OXYGEN ABSORPTION BANDS IN THE DISK-INTEGRATED SPECTRA OF EARTH

    International Nuclear Information System (INIS)

    Fujii, Yuka; Suto, Yasushi; Turner, Edwin L.

    2013-01-01

    We study the variability of major atmospheric absorption features in the disk-integrated spectra of Earth with future application to Earth-analogs in mind, concentrating on the diurnal timescale. We first analyze observations of Earth provided by the EPOXI mission, and find 5%-20% fractional variation of the absorption depths of H 2 O and O 2 bands, two molecules that have major signatures in the observed range. From a correlation analysis with the cloud map data from the Earth Observing Satellite (EOS), we find that their variation pattern is primarily due to the uneven cloud cover distribution. In order to account for the observed variation quantitatively, we consider a simple opaque cloud model, which assumes that the clouds totally block the spectral influence of the atmosphere below the cloud layer, equivalent to assuming that the incident light is completely scattered at the cloud top level. The model is reasonably successful, and reproduces the EPOXI data from the pixel-level EOS cloud/water vapor data. A difference in the diurnal variability patterns of H 2 O and O 2 bands is ascribed to the differing vertical and horizontal distribution of those molecular species in the atmosphere. On Earth, the inhomogeneous distribution of atmospheric water vapor is due to the existence of its exchange with liquid and solid phases of H 2 O on the planet's surface on a timescale short compared with atmospheric mixing times. If such differences in variability patterns were detected in spectra of Earth-analogs, it would provide the information on the inhomogeneous composition of their atmospheres.

  1. Specific absorption spectra of hemoglobin at different PO2 levels: potential noninvasive method to detect PO2 in tissues.

    Science.gov (United States)

    Liu, Peipei; Zhu, Zhirong; Zeng, Changchun; Nie, Guang

    2012-12-01

    Hemoglobin (Hb), as one of main components of blood, has a unique quaternary structure. Its release of oxygen is controlled by oxygen partial pressure (PO2). We investigate the specific spectroscopic changes in Hb under different PO2 levels to optimize clinical methods of measuring tissue PO2. The transmissivity of Hb under different PO2 levels is measured with a UV/Vis fiber optic spectrometer. Its plotted absorption spectral curve shows two high absorption peaks at 540 and 576 nm and an absorption valley at 560 nm when PO2 is higher than 100 mm Hg. The two high absorption peaks decrease gradually with a decrease in PO2, whereas the absorption valley at 560 nm increases. When PO2 decreases to approximately 0 mm Hg, the two high absorption peaks disappear completely, while the absorption valley has a hypochromic shift (8 to 10 nm) and forms a specific high absorption peak at approximately 550 nm. The same phenomena can be observed in visible reflectance spectra of finger-tip microcirculation. Specific changes in extinction coefficient and absorption spectra of Hb occur along with variations in PO2, which could be used to explain pathological changes caused by tissue hypoxia and for early detection of oxygen deficiency diseases in clinical monitoring.

  2. A reaction cell for ambient pressure soft x-ray absorption spectroscopy

    Science.gov (United States)

    Castán-Guerrero, C.; Krizmancic, D.; Bonanni, V.; Edla, R.; Deluisa, A.; Salvador, F.; Rossi, G.; Panaccione, G.; Torelli, P.

    2018-05-01

    We present a new experimental setup for performing X-ray Absorption Spectroscopy (XAS) in the soft X-ray range at ambient pressure. The ambient pressure XAS setup is fully compatible with the ultra high vacuum environment of a synchrotron radiation spectroscopy beamline end station by means of ultrathin Si3N4 membranes acting as windows for the X-ray beam and seal of the atmospheric sample environment. The XAS detection is performed in total electron yield (TEY) mode by probing the drain current from the sample with a picoammeter. The high signal/noise ratio achievable in the TEY mode, combined with a continuous scanning of the X-ray energies, makes it possible recording XAS spectra in a few seconds. The first results show the performance of this setup to record fast XAS spectra from sample surfaces exposed at atmospheric pressure, even in the case of highly insulating samples. The use of a permanent magnet inside the reaction cell enables the measurement of X-ray magnetic circular dichroism at ambient pressure.

  3. Signatures in vibrational and UV-visible absorption spectra for identifying cyclic hydrocarbons by graphene fragments.

    Science.gov (United States)

    Meng, Yan; Wu, Qi; Chen, Lei; Wangmo, Sonam; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin; Ding, Dajun; Niehaus, Thomas A; Frauenheim, Thomas

    2013-12-21

    To promote possible applications of graphene in molecular identification based on stacking effects, in particular in recognizing aromatic amino acids and even sequencing nucleobases in life sciences, we comprehensively study the interaction between graphene segments and different cyclic organic hydrocarbons including benzene (C6H6), cyclohexane (C6H12), benzyne (C6H4), cyclohexene (C6H10), 1,3-cyclohexadiene (C6H8(1)) and 1,4-cyclohexadiene (C6H8(2)), using the density-functional tight-binding (DFTB) method. Interestingly, we find obviously different characteristics in Raman vibrational and ultraviolet visible absorption spectra of the small molecules adsorbed on the graphene sheet. Specifically, we find that both spectra involve clearly different characteristic peaks, belonging to the different small molecules upon adsorption, with the ones of ionized molecules being more substantial. Further analysis shows that the adsorptions are almost all due to the presence of dispersion energy in neutral cases and involve charge transfer from the graphene to the small molecules. In contrast, the main binding force in the ionic adsorption systems is the electronic interaction. The results present clear signatures that can be used to recognize different kinds of aromatic hydrocarbon rings on graphene sheets. We expect that our findings will be helpful for designing molecular recognition devices using graphene.

  4. Investigation of absorption spectra of Gafchromic EBT2 film's components and their impact on UVR dosimetry

    Science.gov (United States)

    Aydarous, Abdulkadir

    2016-05-01

    The absorption spectra of the EBT2 film's components were investigated in conjunction with its use for UVA dosimetry. The polyester (topside) and adhesive layers of the EBT2 film have been gently removed. Gafchromic™ EBT2 films with and without the protected layers (polyester and adhesive) were exposed to UVR of 365 nm for different durations. Thereafter, the UV-visible spectra were measured using a UV-visible spectrophotometer (Model Spectro Dual Split Beam, UVS-2700). Films were digitized using a Nikon CanoScan 9000F Mark II flatbed scanner. The dosimetric characteristics including film's uniformity, reproducibility and post-irradiation development were investigated. The color development of EBT2 and new modified EBT2 (EBT2-M) films irradiated with UVA was relatively stable (less than 1%) immediately after exposure. Based on this study, the sensitivity of EBT2 to UVR with wavelength between ~350 nm and ~390 nm can significantly be enhanced if the adhesive layer (~25 μm) is removed. The polyester layer plays almost no part on absorbing UVR with wavelength between ~320 nm and ~390 nm. Furthermore, various sensitivities for the EBT2-M film has been established depending on the wavelength of analysis.

  5. Total Absorption Spectroscopy of Fission Fragments Relevant for Reactor Antineutrino Spectra and Decay Heat Calculations

    Directory of Open Access Journals (Sweden)

    Porta A.

    2016-01-01

    Full Text Available Beta decay of fission products is at the origin of decay heat and antineutrino emission in nuclear reactors. Decay heat represents about 7% of the reactor power during operation and strongly impacts reactor safety. Reactor antineutrino detection is used in several fundamental neutrino physics experiments and it can also be used for reactor monitoring and non-proliferation purposes. 92,93Rb are two fission products of importance in reactor antineutrino spectra and decay heat, but their β-decay properties are not well known. New measurements of 92,93Rb β-decay properties have been performed at the IGISOL facility (Jyväskylä, Finland using Total Absorption Spectroscopy (TAS. TAS is complementary to techniques based on Germanium detectors. It implies the use of a calorimeter to measure the total gamma intensity de-exciting each level in the daughter nucleus providing a direct measurement of the beta feeding. In these proceedings we present preliminary results for 93Rb, our measured beta feedings for 92Rb and we show the impact of these results on reactor antineutrino spectra and decay heat calculations.

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

    Science.gov (United States)

    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.

  7. Source brightness fluctuation correction of solar absorption fourier transform mid infrared spectra

    Directory of Open Access Journals (Sweden)

    T. Ridder

    2011-06-01

    Full Text Available The precision and accuracy of trace gas observations using solar absorption Fourier Transform infrared spectrometry depend on the stability of the light source. Fluctuations in the source brightness, however, cannot always be avoided. Current correction schemes, which calculate a corrected interferogram as the ratio of the raw DC interferogram and a smoothed DC interferogram, are applicable only to near infrared measurements. Spectra in the mid infrared spectral region below 2000 cm−1 are generally considered uncorrectable, if they are measured with a MCT detector. Such measurements introduce an unknown offset to MCT interferograms, which prevents the established source brightness fluctuation correction. This problem can be overcome by a determination of the offset using the modulation efficiency of the instrument. With known modulation efficiency the offset can be calculated, and the source brightness correction can be performed on the basis of offset-corrected interferograms. We present a source brightness fluctuation correction method which performs the smoothing of the raw DC interferogram in the interferogram domain by an application of a running mean instead of high-pass filtering the corresponding spectrum after Fourier transformation of the raw DC interferogram. This smoothing can be performed with the onboard software of commercial instruments. The improvement of MCT spectra and subsequent ozone profile and total column retrievals is demonstrated. Application to InSb interferograms in the near infrared spectral region proves the equivalence with the established correction scheme.

  8. Vacuum ultraviolet photochemistry of CH4 and isotopomers. II. Product channel fields and absorption spectra

    International Nuclear Information System (INIS)

    Wang, Jen-Han; Liu, Kopin; Min, Zhiyuan; Su, Hongmei; Bersohn, Richard; Preses, Jack; Larese, John Z.

    2000-01-01

    In part I of this work the relative velocities and anisotropies of the atomic H and D fragments from methane photolysis at 10.2 eV were measured. In this paper the relative abundance of the methyl and methylene fragments are reported. A complete set of quantum yields for the different photodissociation channels of each isotopomer is obtained by combining the two sets of data. Previously it was found that H atoms are almost four times more likely than D atoms to be ejected; now it is found that hydrogen molecule photofragments are much richer in H atoms than in D. Overall, the heavier D atoms are more likely than the H atoms to remain attached to the carbon atom. An implication for astrophysics is discussed. The VUV absorption spectra of CH 4 and CH 3 D are almost identical both at room temperature and 75 K. There is, as expected, no variation in the absorption spectrum with temperature. Evidence is given that all or almost all of the methylene is produced in the a 1 A 1 and not in the ground 3 B 1 state. (c) 2000 American Institute of Physics

  9. Computing the Absorption and Emission Spectra of 5-Methylcytidine in Different Solvents: A Test-Case for Different Solvation Models.

    Science.gov (United States)

    Martínez-Fernández, L; Pepino, A J; Segarra-Martí, J; Banyasz, A; Garavelli, M; Improta, R

    2016-09-13

    The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption and the emission maximum in water are significantly blue-shifted (0.08 eV). The absorption spectra are simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with three different approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) a mixed QM/MM static approach, and (iii) a QM/MM method exploiting the structures issuing from molecular dynamics classical simulations. Ab-initio Molecular dynamics simulations based on CAM-B3LYP functionals have also been performed. The adopted approaches all reproduce the main features of the experimental spectra, giving insights on the chemical-physical effects responsible for the solvent shifts in the spectra of 5-methylcytidine and providing the basis for discussing advantages and limitations of the adopted solvation models.

  10. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  11. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy

    DEFF Research Database (Denmark)

    Grunwaldt, Jan-Dierk; Kimmerle, B.; Baiker, A.

    2009-01-01

    available techniques, X-ray absorption spectroscopy (XAS) is a well-suited tool for this purpose as the different selected examples highlight. Two different techniques, scanning and full-field X-ray microscopy/tomography, are described and compared. At first, the tomographic structure of impregnated alumina...... pellets is presented using full-field transmission microtomography and compared to the results obtained with a scanning X-ray microbeam technique to analyse the catalyst bed inside a catalytic quartz glass reactor. On the other hand, by using XAS in scanning microtomography, the structure...... metal-based catalysts. In order to obtain spectroscopic information on the spatial variation of the oxidation state of the catalyst inside the reactor XAS spectra were recorded by scanning with a micro-focussed beam along the catalyst bed. Alternatively, full-field transmission imaging was used...

  12. Characterization of Monodispersed Iron Oxide Nanocrystals by XAS and MCD measurement

    International Nuclear Information System (INIS)

    Kim, J.-Y.; Noh, H.-J.; Park, B.-G.; Kim, T.-Y.; Park, J.-H.; Hyeon, T.; Park, J.; Kang, E.

    2004-01-01

    Full text: Nanoparticles have attracted so much attention because of their potential technological applications and abundance of scientifically interesting issues. In particular, magnetic nanoparticles are considered to be applicable to various magnetic devices such as terabit memory, ferrofluids, magnetocaloric refrigeration systems, blood cells, etc. With the development of nano-technology, variation of physical properties as a function of particle size is one of the most important issues, but has been rarely explored because of difficulty of the size control in synthesizing nanoparticles. Recently, some of us successfully synthesized high crystalline and monodisperse maghemite nanoparticles without a size selection process and research in this field seems to be promoted by one step. In this report, we present a systematic characterization of the monodispersed nanocrystalline γ - Fe 2 O 3 with the diameter of 13, 8 and 4 nm by measuring the x-ray absorption spectroscopy (XAS) and the x-ray magnetic circular dichroism(XMCD) spectra on Fe L edge. The spectra of the 4 nm nanoparticles are very similar to those of maghemite (γ - Fe 2 O 3 ). However, the spectra become close to those of magnetite (Fe 3 O 4 ) as the particle size becomes 8 and 13 nm. Considering that the maghemite and magnetite have the same spinel structure with different Fe vacancies, these results can be explained that the surface of nanoparticles has more vacancies than the core part, indicating that surface disorder increases as the particle size decreases

  13. Soft X-ray absorption spectra of aqueous salt solutions with highly charged cations in liquid microjets

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.

    2010-03-11

    X-ray absorption spectra of 1M aqueous solutions of indium (III) chloride, yttrium (III) bromide, lanthanum (III) chloride, tin (IV) chloride and chromium (III) chloride have been measured at the oxygen K-edge. Relatively minor changes are observed in the spectra compared to that of pure water. SnCl{sub 4} and CrCl{sub 3} exhibit a new onset feature which is attributed to formation of hydroxide or other complex molecules in the solution. At higher energy, only relatively minor, but salt-specific changes in the spectra occur. The small magnitude of the observed spectral changes is ascribed to offsetting perturbations by the cations and anions.

  14. Pitfalls and artifacts in measuring absorption spectra and kinetics: the effect of stray light in the UV and red regions

    International Nuclear Information System (INIS)

    Czapski, Gideon; Ozeri, Yair; Goldstein, Sara

    2005-01-01

    Effects of stray light on absorption spectrum and kinetics are discussed. The extent of the stray light depends on the light source, monochromator, wavelength set by the instrument and the absorption of the sample at this wavelength. Effects of the stray light on the shape of the spectrum and the extinction coefficients are shown. Methods for determining the existence and extent of stray light are suggested and are especially relevant for studies using pulse radiolysis, flash photolysis, and stopped-flow techniques. The literature examples for artifacts due to stray light are presented for kinetics and absorption spectra

  15. Absorption spectra of H2-H2 pairs in the fundamental band

    International Nuclear Information System (INIS)

    Meyer, W.; Borysow, A.; Frommhold, L.

    1989-01-01

    For the computation of the induced-dipole moment, the collisional complex consisting of two H 2 molecules is treated like one molecule in the self-consistent-field and size-consistent, coupled electron pair approximations that separates correctly at distant range. The basis set accounts for 95% of the correlation energies. The radial transition matrix elements of the induced-dipole components are obtained for the two cases v 1 =v 2 =0 and v 1 =0,v 2 =1, where the v i are the vibrational quantum numbers of the interacting H 2 molecules (i=1 or 2). The dependence of these elements on the most important rotational states (j 1 , j 1 ',j 2 ,j 2 '=0,...,3) involved is obtained and seen to be significant in the fundamental band. The results are recast in a simple, but accurate analytical form that is used in a quantum formalism for computations of the spectral moments (sum rules) and line shapes of the collision-induced absorption spectra of molecular hydrogen pairs in the infrared 2.4-μm band. The calculations are based on a proven isotropic potential model that we have extended to account for effects of vibrational excitations. Numerical consistency of the line-shape calculations with the sum rules is observed at the 1% level. The comparison of the computational results with the available measurements at temperatures from 20 to 300 K shows agreement within the estimated uncertainties of the best measurements (∼10%). This fact suggests that theory is capable of predicting these spectra reliably at temperatures for which no measurements exist, with an accuracy that compares favorably with that of good laboratory measurements

  16. The effects of solvents and structure on the electronic absorption spectra of the isomeric pyridine carboxylic acid N-oxides

    Directory of Open Access Journals (Sweden)

    Drmanić Saša Ž.

    2013-01-01

    Full Text Available The ultraviolet absorption spectra of the carboxyl group of three isomeric pyridine carboxylic acids N-oxides (picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide were determined in fourteen solvents in the wavelength range from 200 to 400 nm. The position of the absorption maxima (λmax of the examined acids showed that the ultraviolet absorption maximum wavelengths of picolinic acid N-oxide are the shortest, and those of isonicotinic acid N-oxide acid are the longest. In order to analyze the solvent effect on the obtained absorption spectra, the ultraviolet absorption frequencies of the electronic transitions in the carboxylic group of the examined acids were correlated using a total solvatochromic equation of the form max = v0 + sπ + aα+ bβ, where υmax is the absorption frequency (1/λmax, p is a measure of the solvent polarity, β represents the scale of solvent hydrogen bond acceptor basicities and α represent the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The solvent effects on the ultraviolet absorption maximums of the examined acids were discussed.

  17. The TApIR experiment. IR absorption spectra of liquid hydrogen isotopologues; Das TApIR Experiment IR-Absorptionsspektren fluessiger Wasserstoffisotopologe

    Energy Technology Data Exchange (ETDEWEB)

    Groessle, Robin

    2015-11-27

    The scope of the thesis is the infrared absorption spectroscopy of liquid hydrogen isotopologues with the tritium absorption infrared spectroscopy (TApIR) experiment at the tritium laboratory Karlsruhe (TLK). The calibration process from the sample preparation to the reference measurements are described. A further issue is the classical evaluation of FTIR absorption spectra and the extension using the rolling circle filter (RCF) including the effects on statistical and systematical errors. The impact of thermal and nuclear spin temperature on the IR absorption spectra is discussed. An empirical based modeling for the IR absorption spectra of liquid hydrogen isotopologues is performed.

  18. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.

    1994-01-01

    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR...

  19. Calculations of magnetic x-ray dichroism in the 3d absorption spectra of rare-earth compounds

    NARCIS (Netherlands)

    GOEDKOOP, JB; THOLE, BT; VANDERLAAN, G; SAWATZKY, GA; DEGROOT, FMF; FUGGLE, JC; de Groot, Frank|info:eu-repo/dai/nl/08747610X

    1988-01-01

    We present atomic calculations for the recently discovered magnetic x-ray dichroism (MXD) displayed by the 3d x-ray-absorption spectra of rare-earth compounds. The spectral shapes expected at T=0 K for linear polarization parallel and normal to the local magnetic field is given, together with the

  20. Exploration of faint absorption bands in the reflectance spectra of the asteroids by method of optimal smoothing: Vestoids

    Science.gov (United States)

    Shestopalov, D. I.; McFadden, L. A.; Golubeva, L. F.

    2007-04-01

    An optimization method of smoothing noisy spectra was developed to investigate faint absorption bands in the visual spectral region of reflectance spectra of asteroids and the compositional information derived from their analysis. The smoothing algorithm is called "optimal" because the algorithm determines the best running box size to separate weak absorption bands from the noise. The method is tested for its sensitivity to identifying false features in the smoothed spectrum, and its correctness of forecasting real absorption bands was tested with artificial spectra simulating asteroid reflectance spectra. After validating the method we optimally smoothed 22 vestoid spectra from SMASS1 [Xu, Sh., Binzel, R.P., Burbine, T.H., Bus, S.J., 1995. Icarus 115, 1-35]. We show that the resulting bands are not telluric features. Interpretation of the absorption bands in the asteroid spectra was based on the spectral properties of both terrestrial and meteorite pyroxenes. The bands located near 480, 505, 530, and 550 nm we assigned to spin-forbidden crystal field bands of ferrous iron, whereas the bands near 570, 600, and 650 nm are attributed to the crystal field bands of trivalent chromium and/or ferric iron in low-calcium pyroxenes on the asteroids' surface. While not measured by microprobe analysis, Fe 3+ site occupancy can be measured with Mössbauer spectroscopy, and is seen in trace amounts in pyroxenes. We believe that trace amounts of Fe 3+ on vestoid surfaces may be due to oxidation from impacts by icy bodies. If that is the case, they should be ubiquitous in the asteroid belt wherever pyroxene absorptions are found. Pyroxene composition of four asteroids of our set is determined from the band position of absorptions at 505 and 1000 nm, implying that there can be orthopyroxenes in all range of ferruginosity on the vestoid surfaces. For the present we cannot unambiguously interpret of the faint absorption bands that are seen in the spectra of 4005 Dyagilev, 4038

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

    Science.gov (United States)

    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.

  2. Theoretically predicted soft x-ray emission and absorption spectra of graphitic-structured BC2N

    Science.gov (United States)

    Muramatsu, Yasuji

    Theoretical B K, C K and N K x-ray emission/absorption spectra of three possible graphitic-structured BC2N clusters are predicted based on the B2p-, C2p-, and N2p- density-of-states (DOS) calculated by discrete variational (DV)-X[alpha] molecular orbital calculations. Several prominent differences in DOS spectral features among BC2Ns, h-BN, and graphite are confirmed from comparison of calculated B2p-, C2p-, and N2p-DOS spectra. These variations in the spectra allow BC2N structures to be positively identified by high-resolution x-ray emission/absorption spectroscopy in the B K, C K, and N K regions.

  3. A comparison of the modulated microwave absorption spectra of ceramic and powdered YBa2Cu3O7-δ samples

    International Nuclear Information System (INIS)

    Rubins, R.S.; Hutton, S.L.; Drumheller, J.E.; Jeong, D.Y.; Black, T.D.

    1990-01-01

    Flux trapping in the 9.3 GHz modulated microwave absorption spectra observed near 4 K from ceramic and powdered ceramic specimens of two separately prepared YBa 2 Cu 3 O 7-δ samples has been used to separate the intergranular and intragranular contributions to the spectra. In the denser, glassy sample, a broad absorption with a peak near 400 Oe for forward sweeps was observed with appreciable intensity after the maximum flux was trapped. This spectrum is attributed to intergranular junctions, since its relative intensity was reduced on powdering and suspending in wax. In the less dense, more uniform sample, the latter spectrum was appreciably weaker in both ceramic and powder. Both types of junction appear to contribute to the narrow low-field absorption which was observed after zero field cooling in all the samples

  4. Effects of excited state mixing on transient absorption spectra in dimers Application to photosynthetic light-harvesting complex II

    CERN Document Server

    Valkunas, L; Trinkunas, G; Müller, M G; Holzwarth, A R

    1999-01-01

    The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler-London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls...

  5. Optical-absorption spectra associated with shallow donor impurities in GaAs-(Ga,Al)As quantum-dots

    International Nuclear Information System (INIS)

    Silva Valencia, J.

    1995-08-01

    The binding energy of a hydrogenic donor impurity and the optical-absorption spectra associated with transitions between the n=1 valence level and the donor-impurity band were calculated for infinite barrier-well spherical GaAs-(Ga,Al)As quantum-dots of different radii, using the effective mass approximation within a variational scheme. An absorption peak associated with transitions involving impurities at the center of the well and a peak related with impurities at the edge of the dot were the main features observed for the different radii of the dots considered in the calculations. Also as a result of the higher electronic confinement in a quantum- dot, we found a much wider energy range of the absorption spectra when compared to infinite GaAs-(Ga,Al)As quantum-wells and quantum-well wires of width and diameter comparable to the diameter of the quantum dot. (author). 13 refs, 3 figs

  6. XAS studies on selenite reduction by pyrite

    International Nuclear Information System (INIS)

    Kang Mingliang; Liu Chunli; Chen Fanrong; Charlet, Laurnet

    2012-01-01

    The interaction of aqueous Se (IV) with pyrite were systematically investigated in light of thermodynamic calculations and X-ray Absorption Spectroscopy (XAS). The results from the speciation study reveal that the reduction product is Se (O) when natural pyrite reacts with Se (N) at pH≤5.65, while small amount of FeSeO 3 or iron selenides may be formed at pH 6.1. At pH≥6.94, due to the precipitation of Fe (Ⅲ) -oxyhydroxide, the formation of the thermodynamically most stable species, FeSe 2 , is inhibited. However, when the reactive nanopyrite-greigite was used for reaction, the thermodynamically most stable species, FeSe 2 , was found for the first time as the predominant product in the present study, suggesting that 79 Se can be immobilized in its most insoluble form, FeSe 2 , in Fe (Ⅱ) -sulfide containing environment. This study confirms that pyrite can significantly attenuate the mobility of Se by reductive precipitation, and that the reaction process does not produce protons under acidic or neutral condition when Se (O) is formed. (authors)

  7. Time resolved spectra in the infrared absorption and emission from shock heated hydrocarbons

    Science.gov (United States)

    Bauer, S. H.; Borchardt, D. B.

    1990-07-01

    We have extended the wavelength range of our previously constructed multichannel, fast recording spectrometer to the mid-infrared. With the initial configuration, using a silicon-diode (photovoltaic) array, we recorded light intensities simultaneously at 20 adjacent wavelengths, each with 20 μs time resolution. For studies in the infrared the silicon diodes are replaced by a 20 element PbSe (photoconducting) array of similar dimensions (1×4 mm/element), cooled by a three-stage thermoelectric device. These elements have useful sensitivities over 1.0-6.7 μm. Three interchangeable gratings in a 1/4 m monochromator cover the following spectral ranges: 1.0-2.5 μm (resolution 33.6 cm-1) 2.5-4.5 μm (16.8 cm-1) 4.0-6.5 μm (16.7 cm-1). Incorporated in the new housing there are individually controlled bias-power sources for each detector, two stages of analogue amplification and a 20-line parallel output to the previously constructed digitizer, and record/hold computer. The immediate application of this system is the study of emission and absorption spectra of shock heated hydrocarbons-C2H2, C4H4 and C6H6-which are possible precursors of species that generate infrared emissions in the interstellar medium. It has been recently proposed that these radiations are due to PAH that emit in the infrared upon relaxation from highly excited states. However, it is possible that such emissions could be due to shock-heated low molecular-weight hydrocarbons, which are known to be present in significant abundances, ejected into the interstellar medium during stellar outer atmospheric eruptions. The full Swan band system appeared in time-integrated emission spectra from shock heated C2H2 (1% in Ar; T5eq~=2500K) no soot was generated. At low resolution the profiles on the high frequency side of the black body maximum show no distinctive features. These could be fitted to Planck curves, with temperatures that declined with time from an initial high that was intermediate between T5 (no

  8. Study of electron transition energies between anions and cations in spinel ferrites using differential UV–vis absorption spectra

    International Nuclear Information System (INIS)

    Xue, L.C.; Wu, L.Q.; Li, S.Q.; Li, Z.Z.; Tang, G.D.; Qi, W.H.; Ge, X.S.; Ding, L.L.

    2016-01-01

    It is very important to determine electron transition energies (E_t_r) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV–vis absorption spectra using the curve (αhν)"2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV–vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (E_t_r) between the anions and cations, Fe"2"+ and Fe"3"+ at the (A) and [B] sites and Ni"2"+ at the [B] sites for the (A)[B]_2O_4 spinel ferrite samples Co_xNi_0_._7_−_xFe_2_._3O_4 (0.0≤x≤0.3), Cr_xNi_0_._7Fe_2_._3_−_xO_4 (0.0≤x≤0.3) and Fe_3O_4. We suggest that the differential UV–vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  9. Calculation of emission and absorption spectra of LTE plasma by the STA method

    International Nuclear Information System (INIS)

    Oreg, A.B.J.; Goldstein, W.H.

    1991-01-01

    Recent improvements in the Super Transition Array (STA) method for calculating Bound-Bound (BB) and Bound-Free (BF) emission and absorption spectra for LTE plasma are described and illustrated. The method accounts for all possible BB and BF radiative transitions in the plasma. Full detailed first order quantum relativistic treatment is used for calculating transition energies and probabilities. The enormous number of configurations are divided into sets of superconfigurations comprised of a collection of energetically grouped configurations to a specific one-electron transition is then represented by a Gaussian whose moments (total intensity, average energy and variance) are calculated accurately using a technique that bypasses the necessity of direct summation over all the levels involved. The calculation of these moments involves the populations of the configurations given by their statistical weights and the Boltzmann factor. For each configuration within the superconfiguration the authors use zeroeth order energies in the Boltzmann factor corrected by a superconfiguration averaged first order term. The structure of the spectrum is increasingly revealed by splitting each STA into a number of smaller STAs. When the spectrum converges it describes the detailed UTA structure, where each configuration-to-configuration array is represented by a separate Gaussian with first order energy in the Boltzmann factor. Convergence is reached with only a few thousand STAs, at most, which makes the calculations practical. It should be pointed out that in this treatment the STA moments are obtained by summing over all level-to-level transitions, rather than configuration-to-configuration average transitions. The authors also take into account orbital relaxation by calculating orbitals and energies for each superconfiguration in its own, optimized potential

  10. Absorption spectra of trapped holes in anatase TiO2

    DEFF Research Database (Denmark)

    Zawadzki, Pawel

    2013-01-01

    absorption spectroscopy (TAS), but the understanding of the optical absorption due to trapped carriers in TiO2 is incomplete. On the basis of the generalized Δ self-consistent field density functional theory (Δ-SCF DFT) calculations, we attribute the experimentally observed absorption band at 430-550 nm...

  11. XMM-Newton Survey of Local O VII Absorption Lines in the Spectra of Galactic X-Ray Sources

    Science.gov (United States)

    Luo, Yang; Fang, Taotao; Ma, Renyi

    2018-04-01

    The detection of highly ionized metal absorption lines in the X-ray spectra of the Galactic X-ray binaries (XRBs) implies the distribution of hot gas along the sightline toward the background sources. However, the origin of this hot gas is still unclear: it can arise in the hot interstellar medium (ISM), or is intrinsic to the XRBs. In this paper, we present an XMM-Newton survey of the O VII absorption lines in the spectra of Galactic XRBs. A total of 33 XRBs were selected, with 29 low-mass XRBs and 4 high-mass XRBs. At a more than 3σ threshold, O VII absorption line was detected in 16 targets, among which 4 were newly discovered in this work. The average line equivalent width is centered around ∼20 mÅ. Additionally, we do not find strong correlations between the O VII EWs and the Galactic neutral absorption N H, the Galactic coordinates, or the distance of background targets. Such non-correlation may suggest contamination of the circumstellar material, or a lack of constraints on the line Doppler-b parameter. We also find that regardless of the direction of the XRBs, the O VII absorption lines are always detected when the flux of the background XRBs reaches a certain level, suggesting a uniform distribution of this hot gas. We estimate a ratio of 0.004–0.4 between the hot and neutral phases of the ISM. This is the second paper in the series following Fang et al. (2015), in which we focused on the local O VII absorption lines detected in the background AGN spectra. Detailed modeling of the hot ISM distribution will be investigated in a future paper.

  12. Continuum and discrete pulsed cavity ring down laser absorption spectra of Br2 vapor.

    Science.gov (United States)

    Sharma, Ramesh C; Huang, Hong-Yi; Chuang, Wang-Ting; Lin, King-Chuen

    2005-07-01

    The absorption cross-sections at room temperature are reported for the first time, of Br2 vapor in overlapping bound-free and bound-bound transition of A(3)pi1u Br2. We obtained discrete absorption cross-section in the rotational structure, the continuum absorption cross-sections, and were also able to measure the absorption cross-section in separate contribution of A(3)pi1u Br2. The absorption cross-sections are increasing with increasing excitation energy in the wavelength region 510-535 nm.

  13. Exciton dynamics in GaAs/AlxGa1-xAs quantum wells

    DEFF Research Database (Denmark)

    Litvinenko, K.; Birkedal, Dan; Lyssenko, V. G.

    1999-01-01

    The changes induced in the optical absorption spectrum of a GaAs/AlxGa1-xAs multiple quantum well due to a photoexcited carrier distribution are reexamined. We use a femtosecond pump-probe technique to excite excitons and free electron-hole pairs. We find that for densities up to 10(11) cm(-2...

  14. Time-dependent radiolytic yields at room temperature and temperature-dependent absorption spectra of the solvated electrons in polyols

    International Nuclear Information System (INIS)

    Lin Mingzhang; Mostafavi, M.; Lampre, I.; Muroya, Y.; Katsumura, Y.

    2007-01-01

    The molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol -1 ·m 2 for 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD), respectively. These values are two-third or three-fourth of the value usually reported in the published report. Picosecond pulse radiolysis studies have aided in depicting the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of the water solution. The temperature dependent absorption spectra of the solvated electron in 12ED, 12PD, and 13PD have been also investigated. In all the three solvents, the optical spectra shift to the red with increasing temperature. While the shape of the spectra does not change in 13PD, a widening on the blue side of the absorption band is observed in 12ED and 12PD at elevated temperatures. (authors)

  15. Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

    Science.gov (United States)

    Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

    2002-07-01

    Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

  16. Experimental and theoretical studies of the VUV emission and absorption spectra of H2, HD and D2 molecules

    International Nuclear Information System (INIS)

    Roudjane, M.

    2007-12-01

    The aim of this thesis is to carry out an experimental study of the absorption and emission spectra of the D 2 and HD isotopes, with high resolution, in the VUV domain and to supplement it by a theoretical study of the excited electronic states involved in the observed transitions. The emission spectra of HD and D 2 are produced by Penning discharge source operating under low pressure and are recorded in the spectral range 78 - 170 nm. The recorded spectra contains more than 20.000 lines. The analysis of the spectrum consists in identifying and assigning the lines to the electronic transitions between energy levels of the molecule. The present analysis is based on our theoretical calculations of the ro-vibrational energy levels of the excited electronic states and the transition probabilities from these states towards the energy levels of the fundamental state. The theoretical results are obtained by resolving the coupled equations between the excited electronic states B 1 Σ u 1 , B' 1 Σ u 1 , C 1 Π u 1 and D 1 Π u 1 , taking into account the nonadiabatic couplings between these states, and they are obtained in the adiabatic approximation for the excited electronic states B''B-bar 1 Σ u + , D' 1 Π u 1 and D'' 1 Π u 1 . The equations are resolved using a modern method based on the discretization variables representation method. In addition, we have carried out a study of the absorption spectra of the HD and D 2 molecules

  17. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation.

    Science.gov (United States)

    Moix, Jeremy M; Ma, Jian; Cao, Jianshu

    2015-03-07

    A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters.

  18. pH-dependent absorption spectra of rhodopsin mutant E113Q: On the role of counterions and protein

    Science.gov (United States)

    Xie, Peng; Zhou, Panwang; Alsaedi, Ahmed; Zhang, Yan

    2017-03-01

    The absorption spectra of bovine rhodopsin mutant E113Q in solutions were investigated at the molecular level by using a hybrid quantum mechanics/molecular mechanics (QM/MM) method. The calculations suggest the mechanism of the absorption variations of E113Q at different pH values. The results indicate that the polarizations of the counterions in the vicinity of Schiff base under protonation and unprotonation states of the mutant E113Q would be a crucial factor to change the energy gap of the retinal to tune the absorption spectra. Glu-181 residue, which is close to the chromophore, cannot serve as the counterion of the protonated Schiff base of E113Q in dark state. Moreover, the results of the absorption maximum in mutant E113Q with the various anions (Cl-, Br-, I- and NO3-) manifested that the mutant E113Q could have the potential for use as a template of anion biosensors at visible wavelength.

  19. Theoretical studies on core-level spectra of solids

    International Nuclear Information System (INIS)

    Kotani, Akio

    1995-01-01

    I present a review on theoretical studies of core-level spectra (CLS) in solids. In CLS, the dynamical response of outer electrons to a core hole is reflected through the screening of core hole potential. Impurity Anderson model (IAM) or cluster model is successfully applied to the analysis of X-ray photoemission spectra (XPS) and X-ray absorption spectra (XAS) in f and d electron systems, where the f and d electron states are hybridized with the other valence or conduction electron states. The effect of the core-hole potential in the final state of XPS and XAS plays an important role, as well as the solid state hybridization and intra-atomic multiplet coupling effects. As typical examples, the calculated results for XPS of rare-earth compounds and transition metal compounds are shown, and some discussions are given. As a subject of remarkable progress with high brightness synchrotron radiation sources, I discuss some theoretical aspects of X-ray emission spectra (XES) and their resonant enhancement at the X-ray absorption threshold. Some experimental data and their theoretical analysis are also given. (author)

  20. ABSORPTION-SPECTRA OF HUMAN FETAL AND ADULT OXYHEMOGLOBIN, DE-OXYHEMOGLOBIN, CARBOXYHEMOGLOBIN, AND METHEMOGLOBIN

    NARCIS (Netherlands)

    ZIJLSTRA, WG; MEEUWSENVANDERROEST, WP

    We determined the millimolar absorptivities of the four clinically relevant derivatives of fetal and adult human hemoglobin in the visible and near-infrared spectral range (450-1000 nm). As expected, spectral absorption curves of similar shape were found, but the small differences between fetal and

  1. Effect of optical pumping on absorption spectra for the doppler broadened rubidium

    International Nuclear Information System (INIS)

    Shin, Seo Ro; Noh, Heung Ryoul

    2008-01-01

    The absorption of a laser beam in the Doppler broadened atomic vapor cell is one of the simplest problems in atomic physics. Although many reports on theoretical and experimental studies of linear absorption have been reported, the effect of optical pumping on the absorption coefficient has not been studied in detail. In this presentation, we present a theoretical and experimental study on linear absorption for the Doppler broadened rubidium vapor cell. The absorption coefficient of a σ"+"(or π)polarized laser beam was calculated as a function of the laser frequency for the various laser intensities. The calculated results were compared with the experimental results. Figure 1(a) shows the calculated absorption coefficient of the π polarized laser beam for the transition F"g"=1→F"e"=0,1,2 of the "87"Rb atom. The diameter of the laser beam was 3mm and the intensity was I=0 and I=0.1I"8"(I"8"=16.2W/m"2"). The peak values for various intensities are shown in Fig. 1(b). We found that the absorption coefficient for the transition from the lower hyperfine state decreased with the increased laser intensity, whereas that for the transition from the upper hyperfine state increased(decreased)for the σ"+"(π)polarized laser beam

  2. Research of electronic absorption spectra of benzazols derivatives by ab initio calculations

    Science.gov (United States)

    Irgibaeva, I. S.; Birimzhanova, D. A.; Barashkov, N. N.

    Using the method of density functional theory in approximating B3LYP with the basis set 6-31G* the computations of structures and UV-vis spectra (TDDFT method) of benzazols derivatives were performed. The comparison of estimated electron spectra with the observed ones was made indicating good agreement of theoretically obtained results with experiment. Moreover these compounds have distinctive spectral-luminescent properties (large stokes shift) because of intramolecular proton transfer in excited state.

  3. Theoretical UV absorption spectra of hydrodynamically escaping O{sub 2}/CO{sub 2}-rich exoplanetary atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Gronoff, G.; Mertens, C. J.; Norman, R. B. [NASA LaRC, Hampton, VA (United States); Maggiolo, R. [BIRA-IASB, Avenue Circulaire 3, 1180 Brussels (Belgium); Wedlund, C. Simon [Aalto University School of Electrical Engineering Department of Radio Science and Engineering, P.O. Box 13000, FI-00076 Aalto (Finland); Bell, J. [National Institute of Aerospace, Hampton, VA (United States); Bernard, D. [IPAG, Grenoble (France); Parkinson, C. J. [University of Michigan, MI (United States); Vidal-Madjar, A., E-mail: Guillaume.P.Gronoff@nasa.gov [Observatoire de Paris, Paris (France)

    2014-06-20

    Characterizing Earth- and Venus-like exoplanets' atmospheres to determine if they are habitable and how they are evolving (e.g., equilibrium or strong erosion) is a challenge. For that endeavor, a key element is the retrieval of the exospheric temperature, which is a marker of some of the processes occurring in the lower layers and controls a large part of the atmospheric escape. We describe a method to determine the exospheric temperature of an O{sub 2}- and/or CO{sub 2}-rich transiting exoplanet, and we simulate the respective spectra of such a planet in hydrostatic equilibrium and hydrodynamic escape. The observation of hydrodynamically escaping atmospheres in young planets may help constrain and improve our understanding of the evolution of the solar system's terrestrial planets' atmospheres. We use the dependency of the absorption spectra of the O{sub 2} and CO{sub 2} molecules on the temperature to estimate the temperature independently of the total absorption of the planet. Combining two observables (two parts of the UV spectra that have a different temperature dependency) with the model, we are able to determine the thermospheric density profile and temperature. If the slope of the density profile is inconsistent with the temperature, then we infer the hydrodynamic escape. We address the question of the possible biases in the application of the method to future observations, and we show that the flare activity should be cautiously monitored to avoid large biases.

  4. Donor-related optical absorption spectra in GaAs-(Ga,Al)As quantum wells: hydrostatic pressure effects

    International Nuclear Information System (INIS)

    Lopez, S.Y.; Duque, C.A.; Porras-Montenegro, N.

    2004-01-01

    Full text: Donor-related optical-absorption spectra for GaAs-(Ga,Al)As quantum wells under hydrostatic pressure are investigated. A variational procedure in the e effective-mass approximation is used in order to obtain binding energies and wave functions. As a general feature, we observe that the binding energy increases with the pressure and with the decreasing of the width of the well. The pressure-related Γ-X crossover has been taken into account in the whole calculation. For the low-pressure regime we observe a linear binding energy behavior, whereas for high pressure the main effect associated with the height of the barrier is the bending of the binding energy curves towards smaller values. Two special structures in the density of impurity states and in the donor-related optical-absorption spectra are observed: an edge associated with transitions involving impurities at the center of the well and a peak associated with transitions related to impurities at the edges of the quantum well. Also, we observe shifts to higher energies of the density of impurity states as a function of the binding energy, as well as changes in the intensity with a red shift of the absorption effect with the hydrostatic pressure. (author)

  5. Laboratory Measurements of Mass Specific Absorption Spectra for Suites of Black Carbon-like, Biomass Burning and Mineral Dust Aerosols

    Science.gov (United States)

    Radney, J.; Zangmeister, C.

    2017-12-01

    Light-absorbing atmospheric aerosols can be grouped into three categories: black carbon (BC), brown carbon (BrC) or mineral dust (MD). In many cases, the absorption of these species is best quantified using a mass-specific absorption cross section (MAC) since the particles are in the Rayleigh regime (BC) or optically thin (BrC and MD); notably, MAC values are both traceable to the SI and transferrable between photoacoustic spectroscopy and filter-based absorption measurements. Here, we present laboratory measurements of MAC for all three light-absorbing aerosol classes. Particles were size- and mass-selected using a differential mobility analyzer and aerosol particle mass analyzer, respectively, with absorption coefficients (αabs) and number concentrations (N) being measured by a broadband photoacoustic spectrometer and condensation particle counter, respectively. This suite of instrumentation allows for direct quantification of MAC from the measured parameters (MAC = αabs/Nmp). Further, the measurements contained > 8 data points spanning λ = 405 nm to 840 nm allowing for spectral curvatures (i.e. the Absorption Angstrom Exponent or AAE) to be fit from many data points versus the more common 2-point interpolations. For the carbonaceous, BC-like aerosols - five samples generated from flames, spark discharge soot (i.e. fullerene soot), graphene, reduced graphene oxide (rGO), and fullerene (C60) - we found: 1) measured MAC ranged between 2.4 m2 g-1 and 8.6 m2 g-1 at λ = 550 nm, 2) most AAEs ranged between 0.5 and 1.3; C60 AAE was 7.5 ± 0.9 and 3) MAC spectra were dependent on fuel type and formation conditions. For BrC particles generated from smoldering combustion of 3 hardwood (Oak, Hickory and Mesquite) and 3 softwood species (Western redcedar, Blue spruce and Baldcypress), we found: 1) median MAC values ranged from 1.4 x 10-2 m2 g-1 to 7.9 x 10-2 m2 g-1 at λ = 550 nm, 2) AAE values ranged between 3.5 and 6.2, and 3) Oak, Western redcedar and Blue spruce

  6. Absorption spectra and Faraday effect in Cs2NaNdCl6 and Cs2NaPrCl6 crystals

    International Nuclear Information System (INIS)

    Ehdel'man, I.S.; Galanov, E.K.; Kokov, I.T.; Malakhovskij, A.V.; Anistratov, A.T.

    1985-01-01

    The paper is devoted to studying absorption spectra and the Faraday effect in Cs 2 NaNdCl 6 and Cs 2 NaPrCl 6 crystals. The absorption spectra and Faraday effect were measured at room temperature in the range of 9000-30000 cmsup(-1) (0.33-1.2 μm) in 0-10 kOe magnetic fields. The absorption spectra produced contain several groups of intense absorption bands resulted from intraconfiguration electron transitions in rare-earth cations. The Faraday spectra in the whole range studied for both crystals have the form of smoothly dipping curves when increasing wavelength. The form of these curves testifies to prevailing contribution of strong electron transitions lying in a nearer UV region to the Faraday effect

  7. An X-ray absorption spectroscopy study of the interactions of Ni2+ with yeast enolase.

    Science.gov (United States)

    Wang, S; Scott, R A; Lebioda, L; Zhou, Z H; Brewer, J M

    1995-05-15

    An x-ray absorption spectroscopy (XAS) study was carried out at pH 7.6 on solutions of Ni2+ and yeast enolase depleted of its physiological cofactor (Mg2+) in the presence or absence of substrate/product, the very strongly bound competitive inhibitor 2-phosphonoacetohydroxamate and Mg2+. Both "conformational" and "catalytic" Ni2+ are distorted octahedral in coordination, in agreement with several spectroscopic studies but in contrast to the coordination in the crystal at pH 6.0. The data are consistent with direct coordination of what must be the catalytic Ni2+ to the phosphate of the substrate, in agreement with some previous data but in disagreement with recent interpretations by other workers. The ligands around the metal ions obtained from the x-ray structure give simulated XAS spectra in good agreement with the observed spectra.

  8. The effect of pathological processes on absorption and scattering spectra of samples of bile and pancreatic juice

    Science.gov (United States)

    Giraev, K. M.; Ashurbekov, N. A.; Magomedov, M. A.; Murtazaeva, A. A.; Medzhidov, R. T.

    2015-07-01

    Spectra of optical transmission coefficients and optical reflectance for bile and pancreatic juice samples were measured experimentally for different forms of pathologies of the pancreas within the range of 250-2500 nm. The absorption and scattering spectra, as well as the spectrum of the anisotropy factor of scattering, were determined based on the results obtained using the reverse Monte Carlo method. The surface morphology for the corresponding samples of the biological media was studied employing electron microscopy. The dynamics of the optical properties of the biological media was determined depending on the stage of the pathology. It has been demonstrated that the results of the study presented are in a good agreement with pathophysiological data and could supplement and broaden the results of conventional methods for diagnostics of the pancreas.

  9. Upper limits for stratospheric H2O2 and HOCl from high resolution balloon-borne infrared solar absorption spectra

    Science.gov (United States)

    Larsen, J. C.; Rinsland, C. P.; Goldman, A.; Murcray, D. G.; Murcray, F. J.

    1985-01-01

    Solar absorption spectra from two stratospheric balloon flights have been analyzed for the presence of H2O2 and HOCl absorption in the 1230.0 to 1255.0 per cm region. The data were recorded at 0.02 per cm resolution during sunset with the University of Denver interferometer system on October 27, 1978 and March 23, 1981. Selected spectral regions were analyzed with the technique of nonlinear least squares spectral curve fitting. Upper limits of 0.33 ppbv for H2O2 and 0.36 ppbv for HOCl near 28 km are derived from the 1978 flight data while upper limits of 0.44 ppbv for H2O2 and 0.43 ppbv for HOCl at 29.5 km are obtained from the 1981 flight data.

  10. Built-in electric field effect on optical absorption spectra of strained (In,Ga)N–GaN nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    El Ghazi, Haddou, E-mail: hadghazi@gmail.com [LPS, Faculty of Science, Dhar EL Mehrez, BP 1796 Fes-Atlas (Morocco); Special Mathematics, CPGE Rabat, Rabat (Morocco); John Peter, A. [Department of Physics, Govt. Arts and Science College, Melur, 625106 Madurai (India)

    2015-08-15

    Based on the effective-mass and the one band parabolic approximations, first order linear, third-order nonlinear and total optical properties related to 1s–1p intra-conduction band transition in wurtzite strained (In,Ga)N–GaN spherical QDs are calculated. The built-in electric field effect, due to the spontaneous and piezoelectric components, is investigated variationally under finite confinement potential. The results reveal that size and internal composition of the dot have a great influence on in-built electric field which affects strongly the optical absorption spectra. It is also found that the modulation of the absorption coefficient, which is suitable for the better performance of optical device applications, can be easily obtained by adjusting geometrical size and internal composition.

  11. Combined effect of solvents and gamma irradiation on the infrared absorption spectra of polyethylene terephthalate

    International Nuclear Information System (INIS)

    Rabie, S.M.; ElBially, A.; Elshourbaguie, S.

    1991-01-01

    The combined effect of solvents and gamma irradiation on the intensities of infrared absorption bands of polyethylene terephthalate, particularly the bands sensitive to conformational changes, were studied. The results revealed that solvent treatment of PET results in significant changes in the intensities of its infrared absorption bands and the exposure of PET to gamma radiation in the presence of solvents helps in the appearance of the two bands at 1550 and 1630 cm . Also, the combined effect of solvents and gamma irradiation on the intensities of the absorption bands is greater than the effect of each agent alone. The extent of the induced changes depends on the nature of solvent and the applied dosage. Further more, for any given solvent or dosage, the rate of change of the intensities of the trans band is not equal to that of the gauche bands.3 fig

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Measurement of energy spectra of charged particles emitted after the absorption of stopped negative pions in carbon

    International Nuclear Information System (INIS)

    Mechtersheimer, G.

    1978-06-01

    The energy spectra of charged particles (p,d,t, 3 He, 4 He and Li-nuclei) emitted after the absorption of stopped negative pions in carbon targets of different thickness (1.227, 0.307, 0.0202 g/cm 2 ) have been measured from the experimental threshold energy of about 0.5 MeV up to the kinematical limit of about 100 MeV. The experiments have been carried out at the biomedical pion channel πE3 of the Swiss Institute of Nuclear Research (SIN). (orig.) [de

  15. Ruthenium(II) chloro-bis(bipyridyl) complexes with substituted pyridine ligands: interpretation of their electronic absorption spectra

    International Nuclear Information System (INIS)

    Sizova, O.V.; Ershov, A.Yu.; Ivanova, N.V.; Shashko, A.D.; Kutejkina-Teplyakova, A.V.

    2003-01-01

    A number of complexes cis-[Ru(Bipy) 2 (L)(Cl)](BF 4 ), where Bipy-2,2'-bipyridine, L-pyridine, 4-aminopyridine, 4-picoline, nicotinamide, isonicotinamide, 3- and 4-cyanopyridine, 4,4'-bipyridine, trans-1,2-bis(4-pyridyl)ethylene, 4,4'-azopyridine, pyrazine, imidazole and NH 3 , were prepared. Using the CINDO-CI semiempirical method the energies and intensities of transition in electronic absorption spectra (EAS) of the complexes were calculated. It is shown that major differences in EAS of the compounds stem from position of transitions with charge transfer d π (Ru)→π*(L) [ru

  16. Second and third peaks in the non-resonant microwave absorption spectra of superconducting Bi2212 crystals

    CSIR Research Space (South Africa)

    Srinivasu, V V

    2010-04-01

    Full Text Available . Bhat, S.V., Ganguly, P., Ramakrishnan, T.V., Rao, C.N.R.: J. Phys. C 20, L559 (1987) 2. Blazey, K.W., Muller, K.A., Bednorz, J.G., Berlinger, W., Amoretti, G., Buluggiu, E., Vera, A., Matacotta, F.C.: Phys. Rev. B 36, 7241 (1987) 3. Kachaturyan, K... 10.1007/s10948-009-0530-5 O R I G I NA L PA P E R Second and Third Peaks in the Non-resonant Microwave Absorption Spectra of Superconducting Bi2212 Crystals V.V. Srinivasu Received: 19 August 2009 / Accepted: 25 August 2009 ' Springer Science...

  17. Novel absorptivity centering method utilizing normalized and factorized spectra for analysis of mixtures with overlapping spectra in different matrices using built-in spectrophotometer software.

    Science.gov (United States)

    Lotfy, Hayam Mahmoud; Omran, Yasmin Rostom

    2018-07-05

    A novel, simple, rapid, accurate, and economical spectrophotometric method, namely absorptivity centering (a-Centering) has been developed and validated for the simultaneous determination of mixtures with partially and completely overlapping spectra in different matrices using either normalized or factorized spectrum using built-in spectrophotometer software without a need of special purchased program. Mixture I (Mix I) composed of Simvastatin (SM) and Ezetimibe (EZ) is the one with partial overlapping spectra formulated as tablets, while mixture II (Mix II) formed by Chloramphenicol (CPL) and Prednisolone acetate (PA) is that with complete overlapping spectra formulated as eye drops. These procedures do not require any separation steps. Resolution of spectrally overlapping binary mixtures has been achieved getting recovered zero-order (D 0 ) spectrum of each drug, then absorbance was recorded at their maxima 238, 233.5, 273 and 242.5 nm for SM, EZ, CPL and PA, respectively. Calibration graphs were established with good correlation coefficients. The method shows significant advantages as simplicity, minimal data manipulation besides maximum reproducibility and robustness. Moreover, it was validated according to ICH guidelines. Selectivity was tested using laboratory-prepared mixtures. Accuracy, precision and repeatability were found to be within the acceptable limits. The proposed method is good enough to be applied to an assay of drugs in their combined formulations without any interference from excipients. The obtained results were statistically compared with those of the reported and official methods by applying t-test and F-test at 95% confidence level concluding that there is no significant difference with regard to accuracy and precision. Generally, this method could be used successfully for the routine quality control testing. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. High covalence in CuSO4 and the radicalization of sulfate: an X-ray absorption and density functional study.

    Science.gov (United States)

    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

  19. Vibrational absorption spectra, DFT and SCC-DFTB conformational study and analysis of [Leu]enkephalin

    DEFF Research Database (Denmark)

    Abdali, Salim; Niehaus, T.A.; Jalkanen, Karl J.

    2003-01-01

    . Ab initio (DFT at the B3LYP/6-31G* level of theory) and semi-empirical (SCC-DFTB) with and without dispersion correction were applied to simulate the VA spectra of [Leu] enkephalin. In these calculations structures taken from X-ray measurements for different conformers of the molecule were used...

  20. The SLUGGS survey: globular cluster stellar population trends from weak absorption lines in stacked spectra

    Science.gov (United States)

    Usher, Christopher; Forbes, Duncan A.; Brodie, Jean P.; Romanowsky, Aaron J.; Strader, Jay; Conroy, Charlie; Foster, Caroline; Pastorello, Nicola; Pota, Vincenzo; Arnold, Jacob A.

    2015-01-01

    As part of the SAGES Legacy Unifying Globulars and GalaxieS (SLUGGS) survey, we stack 1137 Keck DEIMOS (Deep Imaging Multi-Object Spectrograph) spectra of globular clusters from 10 galaxies to study their stellar populations in detail. The stacked spectra have median signal-to-noise ratios of ˜90 Å-1. Besides the calcium triplet, we study weaker sodium, magnesium, titanium and iron lines as well as the Hα and higher order Paschen hydrogen lines. In general, the stacked spectra are consistent with old ages and a Milky Way-like initial mass function. However, we see different metal line index strengths at fixed colour and magnitude, and differences in the calcium triplet-colour relation from galaxy to galaxy. We interpret this as strong evidence for variations in the globular cluster colour-metallicity relation between galaxies. Two possible explanations for the colour-metallicity relation variations are that the average ages of globular clusters vary from galaxy to galaxy or that the average abundances of light elements (i.e. He, C, N and O) differ between galaxies. Stacking spectra by magnitude, we see that the colours become redder and metal line indices stronger with brighter magnitudes. These trends are consistent with the previously reported `blue tilts' being mass-metallicity relations.

  1. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  2. Influence of temperature on water and aqueous glucose absorption spectra in the near- and mid-infrared regions at physiologically relevant temperatures

    DEFF Research Database (Denmark)

    Jensen, P.S.; Bak, J.; Andersson-Engels, S.

    2003-01-01

    transmission cell controlled within 0.02 degreesC. Pathlengths of 50 mum and 0.4 mm were used in the mid- and near-infrared spectral region, respectively. Difference spectra were used to determine the effect of temperature on the water spectra quantitatively. These spectra were obtained by subtracting the 37...... degreesC water spectrum from the spectra measured at other temperatures. The difference spectra reveal that the effect of temperature is highest in the vicinity of the strong absorption bands, with a number of isosbestic points with no temperature dependence and relatively flat plateaus in between......Near- and mid-infrared absorption spectra of pure water and aqueous 1.0 g/dL glucose solutions in the wavenumber range 8000-950 cm(-1) were measured in the temperature range 30-42 C in steps of 2 degreesC. Measurements were carried out with an FT-IR spectrometer and a variable pathlength...

  3. Predicting the Shifts of Absorption Maxima of Azulene Derivatives Using Molecular Modeling and ZINDO CI Calculations of UV-Vis Spectra

    Science.gov (United States)

    Patalinghug, Wyona C.; Chang, Maharlika; Solis, Joanne

    2007-01-01

    The deep blue color of azulene is drastically changed by the addition of substituents such as CH[subscript 3], F, or CHO. Computational semiempirical methods using ZINDO CI are used to model azulene and azulene derivatives and to calculate their UV-vis spectra. The calculated spectra are used to show the trends in absorption band shifts upon…

  4. X-Ray Absorption with Transmission X-Ray Microscopes

    NARCIS (Netherlands)

    de Groot, F.M.F.

    2016-01-01

    In this section we focus on the use of transmission X-ray microscopy (TXM) to measure the XAS spectra. In the last decade a range of soft X-ray and hard X-ray TXM microscopes have been developed, allowing the measurement of XAS spectra with 10–100 nm resolution. In the hard X-ray range the TXM

  5. Extragalactic Background Light expected from photon-photon absorption on spectra of distant Active Galactic Nuclei

    International Nuclear Information System (INIS)

    Sinitsyna, V. G.; Sinitsyna, V. Y.

    2013-01-01

    Extragalactic background radiation blocks the propagation of TeV gamma-ray over large distances by producing e + e - pairs. As a result, primary spectrum of gamma-source is changed, depending on spectrum of background light. So, hard spectra of Active Galactic Nuclei with high red shifts allow the determination of a EBL spectrum. The redshifts of SHALON TeV gamma-ray sources range from 0.018 to 1.375 those spectra are resolved at the energies from 800 GeV to 30 TeV. Spectral energy distribution of EBL constrained from observations of Mkn421 (z=0.031), Mkn501 (z=0.034), Mkn180 (z=0.046), OJ287 (z=0.306), 3c454.3 (z=0.859) and 1739+5220(z=1.375) together with models and measurements are presented. (authors)

  6. Simultaneous infrared and UV-visible absorption spectra of matrix-isolated carbon vapor

    Science.gov (United States)

    Kurtz, Joe; Huffman, Donald R.

    1989-01-01

    Carbon molecules were suggested as possible carriers of the diffuse interstellar bands. In particular, it was proposed that the 443 nm diffuse interstellar band is due to the same molecule which gives rise to the 447 nm absorption feature in argon matrix-isolated carbon vapor. If so, then an associated C-C stretching mode should be seen in the IR. By doing spectroscopy in both the IR and UV-visible regions on the same sample, the present work provides evidence for correlating UV-visible absorption features with those found in the IR. Early data indicates no correlation between the strongest IR feature (1997/cm) and the 447 nm band. Correlation with weaker IR features is being investigated.

  7. Fine hematite particles of Martian interest: absorption spectra and optical constants

    International Nuclear Information System (INIS)

    Marra, A C; Blanco, A; Fonti, S; Jurewicz, A; Orofino, V

    2005-01-01

    Hematite is an iron oxide very important for the study of climatic evolution of Mars. It can occur in two forms: red and grey, mainly depending on the granulometry of the samples. Spectra of bright regions of Mars suggest the presence of red hematite particles. Moreover the Thermal Emission Spectrometer (TES), on board the Mars Global Surveyor mission, has discovered a deposit of crystalline grey hematite in Sinus Meridiani. TES spectra of that Martian region exhibit features at about 18, 23 and 33 μm that are consistent with hematite. Coarse grey hematite is considered strong evidence for longstanding water, while it is unknown whether the formation of fine-grained red hematite requires abundant water. Studies are needed in order to further characterize the spectral properties of the two kinds of hematite. For this reason we have analyzed a sample of submicron hematite particles in the 6.25-50 μm range in order to study the influence of particles size and shape on the infrared spectra. The optical constants of a particulate sample have been derived and compared with published data concerning bulk samples of hematite. Our results seem to indicate that particle shape is an important factor to take into account for optical constants derivation

  8. Modeling of XANES-spectra with the FEFF-program

    Energy Technology Data Exchange (ETDEWEB)

    Bosman, E; Thieme, J, E-mail: e.bosman@gmx.d, E-mail: jthieme@gwdg.d [Institute for X-Ray Physics, Georg-August-University Gottingen, Friedrich-Hund-Platz 1, 37077 Gottingen (Germany)

    2009-09-01

    The aim of this project is the calculation of the absorption coefficient {mu} of x-ray absorption spectra as a function of energy and a comparison with experimental data. A characteristic fine structure can be found in x-ray absorption spectra (XAS) consisting of the XANES (X-Ray Absorption Near Edge Structure) and the EXAFS (Extended X-Ray Absorption Fine Structure) region. XANES is characterized by multiple scattering and provides information about coordination chemistry and bonding angles of the irradiated sample. The program FEFF 8.4 was used for the calculations of the absorption K-edge spectra. FEFF was generated for ab initio multiple scattering calculations of X-ray Absorption Fine Structure (XAFS) of atom-clusters. The code yields scattering amplitudes, phases and other quantities. We computed {mu} at the K-edge of several elements like Ti, S and Fe. For this purpose, clusters of Na{sub 2}SO{sub 4}, Ba{sub 2}TiO{sub 4}, FeS{sub 2}, CaSO{sub 2} 2(H {sub 2}O) were used, working with several space groups. Some of the calculations are consistent with the results of the experiments, but others show energy shifts in the range of some eV. In summary, the FEFF calculations and the experimental data exhibit similarities as well as deviations. By using trimming parameters, deviations could be eliminated to a certain extent, which will be presented.

  9. Triplet--Triplet Absorption Spectra of Organic Molecules in Condensed Phases

    International Nuclear Information System (INIS)

    Carmichael, I.; Hug, G.L.

    1986-01-01

    We present a compilation of spectral parameters associated with triplet--triplet absorption of organic molecules in condensed media. The wavelengths of maximum absorbance and the corresponding extinction coefficients, where known, have been critically evaluated. Other data, for example, lifetimes, energies and energy transfer rates, relevant to the triplet states of these molecules are included by way of comments but have not been subjected to a similar scrutiny. Work in the gas phase has been omitted, as have theoretical studies. We provide an introduction to triplet state processes in solution and solids, developing the conceptual background and offering an historical perspective on the detection and measurement of triplet state absorption. Techniques employed to populate the triplet state are reviewed and the various approaches to the estimation of the extinction coefficient of triplet--triplet absorption are critically discussed. A statistical analysis of the available data is presented and recommendations for a hierarchical choice of extinction coefficients are made. Data collection is expected to be complete through the end of 1984. Compound name, molecular formula and author indexes are appended

  10. Effects of Cations on the Hydrogen Bond Network of Liquid Water: New Results from X-ray Absorption Spectroscopy of Liquid Microjets

    International Nuclear Information System (INIS)

    Cappa, Christopher D.; Smith, Jared D.; Messer, Benjamin M.; Cohen, Ronald C.; Saykally, Richard J.

    2005-01-01

    The oxygen K-edge absorption spectra (XAS) of aqueous chloride solutions are measured for Li + , Na + , K + , NH + , C(NH2) 3 + , Mg 2+ and Ca 2+ and 4 M cation concentrations. Density functional theory calculation have indicated that the ion-specific spectral variations arise from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, as a result of differences in charge transfer from the water molecules onto the divalent cations

  11. Investigation of absorption spectra of Gafchromic EBT2 film's components and their impact on UVR dosimetry

    International Nuclear Information System (INIS)

    Aydarous, Abdulkadir

    2016-01-01

    The absorption spectra of the EBT2 film's components were investigated in conjunction with its use for UVA dosimetry. The polyester (topside) and adhesive layers of the EBT2 film have been gently removed. Gafchromic™ EBT2 films with and without the protected layers (polyester and adhesive) were exposed to UVR of 365 nm for different durations. Thereafter, the UV–visible spectra were measured using a UV–visible spectrophotometer (Model Spectro Dual Split Beam, UVS-2700). Films were digitized using a Nikon CanoScan 9000F Mark II flatbed scanner. The dosimetric characteristics including film's uniformity, reproducibility and post-irradiation development were investigated. The color development of EBT2 and new modified EBT2 (EBT2-M) films irradiated with UVA was relatively stable (less than 1%) immediately after exposure. Based on this study, the sensitivity of EBT2 to UVR with wavelength between ~350 nm and ~390 nm can significantly be enhanced if the adhesive layer (~25 µm) is removed. The polyester layer plays almost no part on absorbing UVR with wavelength between ~320 nm and ~390 nm. Furthermore, various sensitivities for the EBT2-M film has been established depending on the wavelength of analysis. - Highlights: • The absorption spectra of the EBT2 film's components were investigated. • The EBT2 sensitivity to UVR can be enhanced if the adhesive layer is removed. • The polyester layer plays almost no part on absorbing UVA radiation. • The color development of EBT2-M films was almost stable immediately after exposure.

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

    International Nuclear Information System (INIS)

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

    2004-01-01

    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 2 Ge 0.8 Cr 0.2 O 4 , Ba 2 Ge 0.1 Cr 0.9 O 4 , Sr 2 CrO 4 , Ca 2 (PO 4 ) x (CrO 4 ) 1-x Cl (x=0.25,0.5), Ca 5 (CrO 4 ) 3 Cl, CrO 3 , the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3 , CrF 3 , Cr 2 O 3 , KCr(SO 4 ) 2 · 12H 2 O, 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-05-10

    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{sub 2}Ge{sub 0.8}Cr{sub 0.2}O{sub 4}, Ba{sub 2}Ge{sub 0.1}Cr{sub 0.9}O{sub 4}, Sr{sub 2}CrO{sub 4}, Ca{sub 2}(PO{sub 4}){sub x}(CrO{sub 4}){sub 1-x}Cl (x=0.25,0.5), Ca{sub 5}(CrO{sub 4}){sub 3}Cl, CrO{sub 3}, the octahedrally coordinated compounds Cr(II)-acetate, CrCl{sub 3}, CrF{sub 3}, Cr{sub 2}O{sub 3}, KCr(SO{sub 4}){sub 2} {center_dot} 12H{sub 2}O, CrO{sub 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.

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

    Science.gov (United States)

    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.

  15. Emission from water vapor and absorption from other gases at 5-7.5 μm in Spitzer-IRS Spectra Of Protoplanetary Disks

    Energy Technology Data Exchange (ETDEWEB)

    Sargent, B. A. [Center for Imaging Science and Laboratory for Multiwavelength Astrophysics, Rochester Institute of Technology, 54 Lomb Memorial Drive, Rochester, NY 14623 (United States); Forrest, W.; Watson, Dan M.; Kim, K. H.; Richter, I.; Tayrien, C. [Department of Physics and Astronomy, University of Rochester, Rochester, NY 14627 (United States); D' Alessio, P.; Calvet, N. [Department of Astronomy, The University of Michigan, 500 Church Street, 830 Dennison Building, Ann Arbor, MI 48109 (United States); Furlan, E. [National Optical Astronomy Observatory, 950 North Cherry Avenue, Tucson, AZ 85719 (United States); Green, J. [Department of Astronomy, University of Texas, 1 University Station, Austin, TX 78712 (United States); Pontoppidan, K., E-mail: baspci@rit.edu [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States)

    2014-09-10

    We present spectra of 13 T Tauri stars in the Taurus-Auriga star-forming region showing emission in Spitzer Space Telescope Infrared Spectrograph 5-7.5 μm spectra from water vapor and absorption from other gases in these stars' protoplanetary disks. Seven stars' spectra show an emission feature at 6.6 μm due to the ν{sub 2} = 1-0 bending mode of water vapor, with the shape of the spectrum suggesting water vapor temperatures >500 K, though some of these spectra also show indications of an absorption band, likely from another molecule. This water vapor emission contrasts with the absorption from warm water vapor seen in the spectrum of the FU Orionis star V1057 Cyg. The other 6 of the 13 stars have spectra showing a strong absorption band, peaking in strength at 5.6-5.7 μm, which for some is consistent with gaseous formaldehyde (H{sub 2}CO) and for others is consistent with gaseous formic acid (HCOOH). There are indications that some of these six stars may also have weak water vapor emission. Modeling of these stars' spectra suggests these gases are present in the inner few AU of their host disks, consistent with recent studies of infrared spectra showing gas in protoplanetary disks.

  16. An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

    Science.gov (United States)

    Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

    2009-11-21

    We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

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

    Science.gov (United States)

    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.

  18. Use of the SF-8 detection spectrophotometer for measuring absorption spectra of molten salts

    International Nuclear Information System (INIS)

    Kotlin, V.P.; Barbanel', Yu.A.

    1975-01-01

    Three versions of the use of the SF-8 spectrophotometer for high-temperature measurements are described: 1) based on the standard optical scheme at temperatures of up to 400 0 C; 2) based on a modified one-wave scheme; 3) based on a modified twin-wave scheme. The external heater used in the schemes 2 and 3 ensures that measurements can be performed at temperatures of up to 1000 0 C. In order to obtain the spectra of thin-layer samples vessels with an insert are used. For operation of the spectrophotometer according to the schemes 2 and 3 te heater may in principle be replaced by a cryostat or some other external device

  19. Electronic structure and optical absorption spectra of Y2 and Zr2 dimers

    International Nuclear Information System (INIS)

    Gutsev, G.L.

    1989-01-01

    The electron structure, ionization potentials from valent levels and energies of optic transitions of Y 2 and Zr 2 dimers are calculated within the framework of discrete-variatin X α -method. It is shown that the symmetry state 1 Σ g + is the main state of Y 2 and Zr 2 dimers, and the atoms in dimers have high-spin 4d n+1 5s 1 configuration. The chemical binding in Y 2 has the dominating 5s-5s nature which is revealed in a considerable interatomic distance; binding of 4d-electrons brings about a significant decrease in the bond length in Zr 2 dimer. The theoretical spectrum of optical absorption of Zr 2 agrees well with the obtained experimental spectrum of this molecule isolated in the organ matrix

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  2. PHOTOIONIZATION MODELING OF OXYGEN K ABSORPTION IN THE INTERSTELLAR MEDIUM: THE CHANDRA GRATING SPECTRA OF XTE J1817-330

    International Nuclear Information System (INIS)

    Gatuzz, E.; Mendoza, C.; García, J.; Lohfink, A.; Kallman, T. R.; Witthoeft, M.; 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 Å 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 Å) 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 H = 1.38 ± 0.01 × 10 21 cm –2 ; an ionization parameter of log ξ = –2.70 ± 0.023; an oxygen abundance of A O = 0.689 +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 results from previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse and Sauval, a rescaling with the revision by Asplund et al. yields A O =0.952 +0.020 -0.013 , a value close to solar that reinforces the new standard. We identify several atomic absorption lines—Kα, Kβ, and Kγ in O I and O II and Kα in O III, O VI, and O 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 > 2 associated with ISM cold absorption.

  3. Optical absorption spectra and g factor of MgO: Mn2+explored by ab initio and semi empirical methods

    Science.gov (United States)

    Andreici Eftimie, E.-L.; Avram, C. N.; Brik, M. G.; Avram, N. M.

    2018-02-01

    In this paper we present a methodology for calculations of the optical absorption spectra, ligand field parameters and g factor for the Mn2+ (3d5) ions doped in MgO host crystal. The proposed technique combines two methods: the ab initio multireference (MR) and the semi empirical ligand field (LF) in the framework of the exchange charge model (ECM) respectively. Both methods of calculations are applied to the [MnO6]10-cluster embedded in an extended point charge field of host matrix ligands based on Gellé-Lepetit procedure. The first step of such investigations was the full optimization of the cubic structure of perfect MgO crystal, followed by the structural optimization of the doped of MgO:Mn2+ system, using periodic density functional theory (DFT). The ab initio MR wave functions approaches, such as complete active space self-consistent field (CASSCF), N-electron valence second order perturbation theory (NEVPT2) and spectroscopy oriented configuration interaction (SORCI), are used for the calculations. The scalar relativistic effects have also been taken into account through the second order Douglas-Kroll-Hess (DKH2) procedure. Ab initio ligand field theory (AILFT) allows to extract all LF parameters and spin-orbit coupling constant from such calculations. In addition, the ECM of ligand field theory (LFT) has been used for modelling theoptical absorption spectra. The perturbation theory (PT) was employed for the g factor calculation in the semi empirical LFT. The results of each of the aforementioned types of calculations are discussed and the comparisons between the results obtained and the experimental results show a reasonable agreement, which justifies this new methodology based on the simultaneous use of both methods. This study establishes fundamental principles for the further modelling of larger embedded cluster models of doped metal oxides.

  4. Comparison between XAS, AWAXS and DAFS applied to nanometer scale supported metallic clusters. Pt.1; monometallic clusters

    International Nuclear Information System (INIS)

    Bazin, D.C.; Sayers, D.A.

    1993-01-01

    The structural information found using three techniques related to synchrotron radiation are compared. XAS (X-ray Absorption Spectroscopy), AWAXS (Anomalous Wide Angle X-ray Scattering) and DAFS (Diffraction Anomalous Fine Structure) are applied to nanometer scale metallic clusters. (author)

  5. Comparison between XAS, AWAXS and DAFS applied to nanometer scale supported metallic clusters. Pt.2; bimetallic clusters

    International Nuclear Information System (INIS)

    Bazin, D.; Sayers, D.

    1993-01-01

    The structural information obtained using three techniques related to synchrotron radiation are compared. XAS (X-ray Absorption Spectroscopy), AWAXS (Anomalous Wide Angle X-ray Scattering) and DAFS (Diffraction Anomalous Fine Structure) are applied to the study of nanometer scale bimetallic clusters. (author)

  6. Time resolved spectra in the infrared absorption and emission from shock heated hydrocarbons. [in interstellar medium

    Science.gov (United States)

    Bauer, S. H.; Borchardt, D. B.

    1990-01-01

    The wavelength range of a previously constructed multichannel fast recording spectrometer was extended to the mid-infrared. With the initial configuration, light intensities were recorded simultaneously with a silicon-diode array simultaneously at 20 adjacent wavelengths, each with a 20-micron time resolution. For studies in the infrared, the silicon diodes were replaced by a 20-element PbSe array of similar dimensions, cooled by a three-stage thermoelectric device. It is proposed that infrared emissions could be due to shock-heated low molecular-weight hydrocarbons. The full Swan band system appeared in time-integrated emission spectra from shock-heated C2H2; no soot was generated. At low resolution, the profiles on the high-frequency side of the black body maximum show no distinctive features. These could be fitted to Planck curves, with temperatures that declined with time from an initial high that was intermediate between T5 (no conversion) and T5(eq).

  7. Collisional Processing of Comet and Asteroid Surfaces: Velocity Effects on Absorption Spectra

    Science.gov (United States)

    Lederer, S. M.; Jensen, E. A.; Wooden, D. H.; Lindsay, S. S.; Smith, D. C.; Nakamura-Messenger, K.; Keller, L. P.; Cintala, M. J.; Zolensky, M. E.

    2012-01-01

    A new paradigm has emerged where 3.9 Gyr ago, a violent reshuffling reshaped the placement of small bodies in the solar system (the Nice model). Surface properties of these objects may have been affected by collisions caused by this event, and by collisions with other small bodies since their emplacement. These impacts affect the spectrographic observations of these bodies today. Shock effects (e.g., planar dislocations) manifest in minerals allowing astronomers to better understand geophysical impact processing that has occurred on small bodies. At the Experimental Impact Laboratory at NASA Johnson Space Center, we have impacted forsterite and enstatite across a range of velocities. We find that the amount of spectral variation, absorption wavelength, and full width half maximum of the absorbance peaks vary non-linearly with the velocity of the impact. We also find that the spectral variation increases with decreasing crystal size (single solid rock versus granular). Future analyses include quantification of the spectral changes with different impactor densities, temperature, and additional impact velocities. Results on diopside, fayalite, and magnesite can be found in Lederer et al., this meeting.

  8. Absorption Spectra of BaF2 Sm2O3, Sm, Gd, and Ho Plasmas

    Science.gov (United States)

    Martin, Michael; Bastiani-Ceccotti, Serena

    2009-11-01

    Knowledge of the opacities of high Z element plasmas is important in indirect drive ICF and the study of stellar evolution. There are few experimental measurements of this quantity, and its theoretical determination is difficult due to the number of possible bound electron configurations. This study aims to better the theoretical understanding of this parameter by looking at the 3d-4f transitions of BaF2, Sm2O3, Sm, Gd, and Ho plasmas at the LULI2000 facility. The plasmas are produced by radiative heating and are cold, 15 -- 40 eV, and relatively dense, ˜ .01gm/cm^3 A plasma is produced by a .5 ns laser pulse irradiating a gold hohlraum and then probed by an x-ray source created by a gold foil irradiated by a 10 ps laser pulse. The transmission is found with simultaneous source and absorption measurements by an x-ray spectrometer in the 8 - 20 å range We will compare the results with statistical atomic structure codes. From this experiment we will gain further insight into the spectral broadening of neighboring Z elements due to changing plasma temperature and into mixture thermodynamics. This is a first step towards an experimental study of astrophysical domains.

  9. Optical absorption spectra of the uranium (4+) ion in the thorium germanate matrix

    CERN Document Server

    Gajek, Z; Antic-Fidancev, E

    1997-01-01

    Visible and infrared absorption measurements on the U sup 4 sup + ion in tetragonal zircon-type matrix beta-ThGeO sub 4 are reported and analysed in terms of the standard parametrization scheme. The observed 17 main peaks and a number of less intense lines have been assigned and fitted to most of the 32 allowed electric dipole transitions with the root mean square error equal to 65 cm sup - sup 1. The free-ion parameters obtained for the model Hamiltonian, zeta 5f = 1809 cm sup - sup 1 , F sup 2 =43 065 cm sup - sup 1 , F sup 4 =38 977 cm sup - sup 1 and F sup 6 =24 391 cm sup - sup 1 , as well as the corresponding crystal-field parameters, B sub 0 sup 2 =-1790 cm sup - sup 1 , B sub 0 sup 4 =1200 cm sup - sup 1 , B sub 4 sup 4 =3260 cm sup - sup 1 , B sub 0 sup 6 =-3170 cm sup - sup 1 and B sub 4 sup 6 =990 cm sup - sup 1 , agree fairly well with the initial theoretical estimations. The results are discussed in relation to the previous spectroscopic study on the scheelite-type matrix UGeO sub 4. (author)

  10. Optical absorption spectra of the uranium (4+) ion in the thorium germanate matrix

    Science.gov (United States)

    Gajek, Z.; Krupa, J. C.; Antic-Fidancev, E.

    1997-01-01

    Visible and infrared absorption measurements on the 0953-8984/9/2/023/img6 ion in tetragonal zircon-type matrix 0953-8984/9/2/023/img7 are reported and analysed in terms of the standard parametrization scheme. The observed 17 main peaks and a number of less intense lines have been assigned and fitted to most of the 32 allowed electric dipole transitions with the root mean square error equal to 0953-8984/9/2/023/img8. The free-ion parameters obtained for the model Hamiltonian, 0953-8984/9/2/023/img9, 0953-8984/9/2/023/img10, 0953-8984/9/2/023/img11 and 0953-8984/9/2/023/img12, as well as the corresponding crystal-field parameters, 0953-8984/9/2/023/img13, 0953-8984/9/2/023/img14, 0953-8984/9/2/023/img15, 0953-8984/9/2/023/img16 and 0953-8984/9/2/023/img17, agree fairly well with the initial theoretical estimations. The results are discussed in relation to the previous spectroscopic study on the scheelite-type matrix 0953-8984/9/2/023/img18.

  11. Optical absorption spectra of the uranium (4+) ion in the thorium germanate matrix

    Energy Technology Data Exchange (ETDEWEB)

    Gajek, Z. [W Trzebiatowski Institute of Low Temperature and Structure Research, Polish Academy of Sciences, 50-950 Wroclaw, PO Box 937 (Poland); Krupa, J.C. [Laboratoire de Radiochimie, Institut de Physique Nucleaire, BP 1, 91406 Orsay Cedex (France); Antic-Fidancev, E. [Unite P- de Recherche associee au CNRS 210, 1 place A Briand, 92195 Meudon Cedex (France)

    1997-01-13

    Visible and infrared absorption measurements on the U{sup 4+} ion in tetragonal zircon-type matrix {beta}-ThGeO{sub 4} are reported and analysed in terms of the standard parametrization scheme. The observed 17 main peaks and a number of less intense lines have been assigned and fitted to most of the 32 allowed electric dipole transitions with the root mean square error equal to 65 cm{sup -1}. The free-ion parameters obtained for the model Hamiltonian, {zeta}5f = 1809 cm{sup -1}, F{sup 2}=43 065 cm{sup -1}, F{sup 4}=38 977 cm{sup -1} and F{sup 6}=24 391 cm{sup -1}, as well as the corresponding crystal-field parameters, B{sub 0}{sup 2}=-1790 cm{sup -1}, B{sub 0}{sup 4}=1200 cm{sup -1}, B{sub 4}{sup 4}=3260 cm{sup -1}, B{sub 0}{sup 6}=-3170 cm{sup -1} and B{sub 4}{sup 6}=990 cm{sup -1}, agree fairly well with the initial theoretical estimations. The results are discussed in relation to the previous spectroscopic study on the scheelite-type matrix UGeO{sub 4}. (author)

  12. Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures

    Science.gov (United States)

    Almandoz, M. C.; Sancho, M. I.; Blanco, S. E.

    2014-01-01

    The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π*). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.

  13. Physical properties of the interstellar medium using high-resolution Chandra spectra: O K-edge absorption

    Energy Technology Data Exchange (ETDEWEB)

    Gatuzz, E.; Mendoza, C. [Centro de Física, Instituto Venezolano de Investigaciones Científicas (IVIC), P.O. Box 20632, Caracas 1020A (Venezuela, Bolivarian Republic of); García, J. [Harvard-Smithsonian Center for Astrophysics, MS-6, 60 Garden Street, Cambridge, MA 02138 (United States); Kallman, T. R. [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Bautista, M. A.; Gorczyca, T. W., E-mail: egatuzz@ivic.gob.ve, E-mail: claudio@ivic.gob.ve, E-mail: javier@head.cfa.harvard.edu, E-mail: manuel.bautista@wmich.edu, E-mail: thomas.gorczyca@wmich.edu, E-mail: timothy.r.kallman@nasa.gov [Department of Physics, Western Michigan University, Kalamazoo, MI 49008 (United States)

    2014-08-01

    Chandra high-resolution spectra toward eight low-mass Galactic binaries have been analyzed with a photoionization model that is capable of determining the physical state of the interstellar medium. Particular attention is given to the accuracy of the atomic data. Hydrogen column densities are derived with a broadband fit that takes into account pileup effects, and in general are in good agreement with previous results. The dominant features in the oxygen-edge region are O I and O II Kα absorption lines whose simultaneous fits lead to average values of the ionization parameter of log ξ = –2.90 and oxygen abundance of A{sub O} = 0.70. The latter is given relative to the standard by Grevesse and Sauval, but rescaling with the revision by Asplund et al. would lead to an average abundance value fairly close to solar. The low average oxygen column density (N{sub O} = 9.2 × 10{sup 17} cm{sup –2}) suggests a correlation with the low ionization parameters, the latter also being in evidence in the column density ratios N(O II)/N(O I) and N(O III)/N(O I) that are estimated to be less than 0.1. We do not find conclusive evidence for absorption by any other compound but atomic oxygen in our oxygen-edge region analysis.

  14. Simultaneous measurement of quantum yield ratio and absorption ratio between acceptor and donor by linearly unmixing excitation-emission spectra.

    Science.gov (United States)

    Zhang, C; Lin, F; DU, M; Qu, W; Mai, Z; Qu, J; Chen, T

    2018-02-13

    Quantum yield ratio (Q A /Q D ) and absorption ratio (K A /K D ) in all excitation wavelengths used between acceptor and donor are indispensable to quantitative fluorescence resonance energy transfer (FRET) measurement based on linearly unmixing excitation-emission spectra (ExEm-spFRET). We here describe an approach to simultaneously measure Q A /Q D and K A /K D values by linearly unmixing the excitation-emission spectra of at least two different donor-acceptor tandem constructs with unknown FRET efficiency. To measure the Q A /Q D and K A /K D values of Venus (V) to Cerulean (C), we used a wide-field fluorescence microscope to image living HepG2 cells separately expressing each of four different C-V tandem constructs at different emission wavelengths with 435 nm and 470 nm excitation respectively to obtain the corresponding excitation-emission spectrum (S DA ). Every S DA was linearly unmixed into the contributions (weights) of three excitation-emission spectra of donor (W D ) and acceptor (W A ) as well as donor-acceptor sensitisation (W S ). Plot of W S /W D versus W A /W D for the four C-V plasmids from at least 40 cells indicated a linear relationship with 1.865 of absolute intercept (Q A /Q D ) and 0.273 of the reciprocal of slope (K A /K D ), which was validated by quantitative FRET measurements adopting 1.865 of Q A /Q D and 0.273 of K A /K D for C32V, C5V, CVC and VCV constructs respectively in living HepG2 cells. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

  15. XAS study of V2O5/Al2O3 catalysts doped with rare earth oxides

    International Nuclear Information System (INIS)

    Centeno, M.A.; Malet, P.; Capitan, M.J.; Benitez, J.J.; Carrizosa, I.; Odriozola, J.A.

    1995-01-01

    This paper reports on XAS studies of well dispersed V 2 O 5 /Al 2 O 3 and V 2 O 5 /Sm 2 O 3 /Al 2 O 3 samples. XAS spectra at V-K and Sm-L III edges show that the rare earth oxide favours the formation of regular tetrahedral units, [VO 4 ], over the surface of the support. Positions of the preedge peak at the V-K edge, and intensities of the white line at the Sm-L III edge also suggest modifications in the electronic density around V and Sm atoms when they are simultaneously supported over Al 2 O 3 . ((orig.))

  16. Measurements of size and composition of particles in polar stratospheric clouds from infrared solar absorption spectra

    International Nuclear Information System (INIS)

    Kinne, S.; Toon, O.B.; Toon, G.C.; Farmer, C.B.; Browell, E.V.; McCormick, M.P.

    1989-01-01

    The attenuation of solar radiation between 1.8- and 15-μm wavelength was measured with the airborne Jet Propulsion Laboratory Mark IV interferometer during the Airborne Antarctic Ozone Expedition in 1987. The measurements not only provide information about the abundance of stratospheric gases, but also about the optical depths of polar stratospheric clouds (PSCs) at wavelengths of negligible gas absorption. The spectral dependence of the PSC optical depth contains information about PSC particle size and particle composition. Thirty-three PSC cases were analyzed and categorized into two types. Type I clouds contain particles with radii of about 0.5 μm and nitric acid concentrations greater than 40%. Type II clouds contain particles composed of water ice with radii of 6 μm and larger. Cloud altitudes were determined from 1.064-μm backscattering observations of the airborne Langley DIAL lidar system. Based on the PSC geometrical thickness, both mass and particle density were estimated. Type I clouds typically had visible wavelength optical depths of about 0.008, mass densities of about 20 ppb, and about 2 particles/cm 3 . The observed type II clouds had optical depths of about 0.03, mass densities of about 400 ppb mass, and about 0.03 particles/cm 3 . The detected PSC type I clouds extended to altitudes of 21 km and were nearly in the ozone-depleted region of the polar stratosphere. The observed type II cases during September were predominantly found at altitudes below 15 km

  17. Accounting for nanometer-thick adventitious carbon contamination in X-ray absorption spectra of carbon-based materials.

    Science.gov (United States)

    Mangolini, Filippo; McClimon, J Brandon; Rose, Franck; Carpick, Robert W

    2014-12-16

    Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is a powerful technique for characterizing the composition and bonding state of nanoscale materials and the top few nanometers of bulk and thin film specimens. When coupled with imaging methods like photoemission electron microscopy, it enables chemical imaging of materials with nanometer-scale lateral spatial resolution. However, analysis of NEXAFS spectra is often performed under the assumption of structural and compositional homogeneity within the nanometer-scale depth probed by this technique. This assumption can introduce large errors when analyzing the vast majority of solid surfaces due to the presence of complex surface and near-surface structures such as oxides and contamination layers. An analytical methodology is presented for removing the contribution of these nanoscale overlayers from NEXAFS spectra of two-layered systems to provide a corrected photoabsorption spectrum of the substrate. This method relies on the subtraction of the NEXAFS spectrum of the overlayer adsorbed on a reference surface from the spectrum of the two-layer system under investigation, where the thickness of the overlayer is independently determined by X-ray photoelectron spectroscopy (XPS). This approach is applied to NEXAFS data acquired for one of the most challenging cases: air-exposed hard carbon-based materials with adventitious carbon contamination from ambient exposure. The contribution of the adventitious carbon was removed from the as-acquired spectra of ultrananocrystalline diamond (UNCD) and hydrogenated amorphous carbon (a-C:H) to determine the intrinsic photoabsorption NEXAFS spectra of these materials. The method alters the calculated fraction of sp(2)-hybridized carbon from 5 to 20% and reveals that the adventitious contamination can be described as a layer containing carbon and oxygen ([O]/[C] = 0.11 ± 0.02) with a thickness of 0.6 ± 0.2 nm and a fraction of sp(2)-bonded carbon of 0.19 ± 0.03. This

  18. Design of an electrochemical cell for in situ XAS studies

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, N. [Instituto de Quimica, Universidade Estadual de Campinas (UNICAMP), Box 6154, CEP 13083-970, Campinas, SP (Brazil); Morais, J. [Instituto de Fisica, Universidade Federal do Rio Grande do Sul (UFRGS), Avenida Bento Goncalves, 9500, Bairro Agronomia, CP 15051, CEP 91501-970, Porto Alegre, RS (Brazil); Alves, M.C.M. [Instituto de Quimica, Universidade Federal do Rio Grande do Sul (UFRGS), Avenida Bento Goncalves, 9500, Bairro Agronomia, CP 15003, CEP 91501-970, Porto Alegre, RS (Brazil)], E-mail: maria@iq.ufrgs.br

    2007-05-15

    In situ X-ray absorption spectroscopy (XAS) studies have been carried out on the electrochemical insertion of Co metal particles in polypyrrole. This has become possible due to the development of an electrochemical cell to allow XAS studies in fluorescence geometry under steady-state conditions. The experimental set-up allows the in situ monitoring of the structural and electronic changes of the selected atom in a matrix. The project of the electrochemical cell is presented with the results obtained at different stages of the electrochemical process. XANES and EXAFS results showed that the initial stage of the cobalt insertion in polypyrrole took place in an ionic form, like [-[(C{sub 4}H{sub 2}N){sub 3}CH{sub 3}(CH{sub 2}){sub 11}OSO{sub 3}{sup -}]{sub 6}Co{sup 2+}] with posterior reduction to a metallic form. The quantitative analysis of the first shell shows that, at -0.60 V, the cobalt atoms are surrounded by 6 ({+-}0.5) atoms located at 2.12 ({+-}0.05) A with a large Debye-Waller factor ({sigma}{sup 2}) value of 0.0368 ({+-}0.0074). At -0.80 V, two distances of R = 1.99 ({+-}0.01) and R = 2.50 ({+-}0.01) A show the coexistence of cobalt in the oxidized and reduced (Co{sup 0}) forms. The Co-Co distance corresponds to that of bulk cobalt. At -1.20 V, the obtained values of N = 12 ({+-}0.5) and R = 2.56 ({+-}0.01) A and a Debye-Waller factor of 0.0176 ({+-}0.0004) suggest the formation of metallic cobalt in a quite disordered form.

  19. Theoretical study on the electronic and optical properties of bulk and surface (001) InxGa1-xAs

    Science.gov (United States)

    Liu, XueFei; Ding, Zhao; Luo, ZiJiang; Zhou, Xun; Wei, JieMin; Wang, Yi; Guo, Xiang; Lang, QiZhi

    2018-05-01

    The optical properties of surface and bulk InxGa1-xAs materials are compared systematically first time in this paper. The band structures, density of states and optical properties including dielectric function, reflectivity, absorption coefficient, loss function and refractive index of bulk and surface InxGa1-xAs materials are investigated by first-principles based on plane-wave pseudo-potentials method within the LDA approximation. The results agree well with the available theoretical and experimental studies and indicate that the electronic and optical properties of bulk and surface InxGa1-xAs materials are much different, and the results show that the considered optical properties of the both materials vary with increasing indium composition in an opposite way. The calculations show that the optical properties of surface In0.75Ga0.25As material are unexpected to be far from the other two indium compositions of surface InxGa1-xAs materials while the optical properties of bulk InxGa1-xAs materials vary with increasing indium composition in an expected regular way.

  20. Incorporation of Trace Elements in Ancient and Modern Human Bone: An X-Ray Absorption Spectroscopy Study

    Science.gov (United States)

    Pingitore, N. E.; Cruz-Jimenez, G.; Price, T. D.

    2001-12-01

    X-ray absorption spectroscopy (XAS) affords the opportunity to probe the atomic environment of trace elements in human bone. We are using XAS to investigate the mode(s) of incorporation of Sr, Zn, Pb, and Ba in both modern and ancient (and thus possibly altered) human and animal bone. Because burial and diagenesis may add trace elements to bone, we performed XAS analysis on samples of pristine contemporary and ancient, buried human and animal bone. We assume that deposition of these elements during burial occurs by processes distinct from those in vivo, and this will be reflected in their atomic environments. Archaeologists measure strontium in human and animal bone as a guide to diet. Carnivores show lower Sr/Ca ratios than their herbivore prey due to discrimination against Sr relative to Ca up the food chain. In an initial sample suite no difference was observed between modern and buried bone. Analysis of additional buried samples, using a more sensitive detector, revealed significant differences in the distance to the second and third neighbors of the Sr in some of the buried samples. Distances to the first neighbor, oxygen, were similar in all samples. Zinc is also used in paleo-diet studies. Initial x-ray absorption spectroscopy of a limited suite of bones did not reveal any differences between modern and buried samples. This may reflect the limited number of samples examined or the low levels of Zn in typical aqueous solutions in soils. Signals from barium and lead were too low to record useful XAS spectra. Additional samples will be studied for Zn, Ba, and Pb. We conducted our XAS experiments on beam lines 4-1 and 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a Lytle detector and appropriate filter, and a solid state, 13-element Ge-detector.

  1. Artificial intelligence applied to the automatic analysis of absorption spectra. Objective measurement of the fine structure constant

    Science.gov (United States)

    Bainbridge, Matthew B.; Webb, John K.

    2017-06-01

    A new and automated method is presented for the analysis of high-resolution absorption spectra. Three established numerical methods are unified into one `artificial intelligence' process: a genetic algorithm (Genetic Voigt Profile FIT, gvpfit); non-linear least-squares with parameter constraints (vpfit); and Bayesian model averaging (BMA). The method has broad application but here we apply it specifically to the problem of measuring the fine structure constant at high redshift. For this we need objectivity and reproducibility. gvpfit is also motivated by the importance of obtaining a large statistical sample of measurements of Δα/α. Interactive analyses are both time consuming and complex and automation makes obtaining a large sample feasible. In contrast to previous methodologies, we use BMA to derive results using a large set of models and show that this procedure is more robust than a human picking a single preferred model since BMA avoids the systematic uncertainties associated with model choice. Numerical simulations provide stringent tests of the whole process and we show using both real and simulated spectra that the unified automated fitting procedure out-performs a human interactive analysis. The method should be invaluable in the context of future instrumentation like ESPRESSO on the VLT and indeed future ELTs. We apply the method to the zabs = 1.8389 absorber towards the zem = 2.145 quasar J110325-264515. The derived constraint of Δα/α = 3.3 ± 2.9 × 10-6 is consistent with no variation and also consistent with the tentative spatial variation reported in Webb et al. and King et al.

  2. Electronic structures of B 2p and C 2p levels in boron-doped diamond films studied using soft x-ray absorption and emission spectroscopy

    Science.gov (United States)

    Nakamura, Jin; Kabasawa, Eiki; Yamada, Nobuyoshi; Einaga, Yasuaki; Saito, Daisuke; Isshiki, Hideo; Yugo, Shigemi; Perera, Rupert C. C.

    2004-12-01

    X-ray absorption (XAS) and emission (XES) spectroscopy near B K and C K edges have been performed on metallic ( ˜0.1at.% B, B-diamond) and semiconducting ( ˜0.03at.% B and N, BN-diamond) doped diamond films. Both B K XAS and XES spectra show a metallic partial density of states (PDOS) with the Fermi energy of 185.3eV , and there is no apparent boron-concentration dependence in contrast to the different electric property. In C K XAS spectrum of B-diamond, the impurity state ascribed to boron is clearly observed near the Fermi level. The Fermi energy is found to be almost same with the top of the valence band of nondoped diamond: EV=283.9eV . C K XAS of BN-diamond shows both the B-induced shallow level and N-induced deep and broad levels as the in-gap states, in which the shallow level is in good agreement with the activation energy (Ea=0.37eV) estimated from the temperature dependence of the conductivity; namely, the change in C2p PDOS of impurity-induced metallization is directly observed. The electric property of this diamond is ascribed mainly to the electronic structure of C2p near the Fermi level. The observed XES spectra are compared with the discrete variational Xα ( DVXα ) cluster calculation. The DVXα result supports the strong hybridization between B2p and C2p observed in XAS and XES spectra, and suggests that the small amount of boron (⩽0.1at.%) in diamond occupies the substitutional site rather than interstitial site.

  3. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X 1Ag ↔ A1B1u absorption and fluorescence spectra of perylene

    International Nuclear Information System (INIS)

    Wang, Chen-Wen; Zhu, Chaoyuan; Lin, Sheng-Hsien; Yang, Ling; Yu, Jian-Guo

    2014-01-01

    Damped harmonic oscillators are utilized to calculate Franck-Condon factors within displaced harmonic oscillator approximation. This is practically done by scaling unperturbed Hessian matrix that represents local modes of force constants for molecule in gaseous phase, and then by diagonalizing perturbed Hessian matrix it results in direct modification of Huang–Rhys factors which represent normal modes of solute molecule perturbed by solvent environment. Scaling parameters are empirically introduced for simulating absorption and fluorescence spectra of an isolated solute molecule in solution. The present method is especially useful for simulating vibronic spectra of polycyclic aromatic hydrocarbon molecules in which hydrogen atom vibrations in solution can be scaled equally, namely the same scaling factor being applied to all hydrogen atoms in polycyclic aromatic hydrocarbons. The present method is demonstrated in simulating solvent enhanced X 1 A g ↔ A 1 B 1u absorption and fluorescence spectra of perylene (medium-sized polycyclic aromatic hydrocarbon) in benzene solution. It is found that one of six active normal modes v 10 is actually responsible to the solvent enhancement of spectra observed in experiment. Simulations from all functionals (TD) B3LYP, (TD) B3LYP35, (TD) B3LYP50, and (TD) B3LYP100 draw the same conclusion. Hence, the present method is able to adequately reproduce experimental absorption and fluorescence spectra in both gas and solution phases

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

    Science.gov (United States)

    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.

  5. Absorption spectra and cyclic voltammograms of uranium species in molten lithium molybdate-sodium molybdate eutectic at 550 C

    International Nuclear Information System (INIS)

    Nagai, T.; Fukushima, M.; Myochin, M.; Uehara, A.; Fujii, T.; Yamana, H.; Sato, N.

    2011-01-01

    Absorption spectra of uranium species dissolved in molten lithium molybdate.sodium molybdate eutectic of 0.51Li 2 MoO 4 -0.49Na 2 MoO 4 mixture at 550 C were measured by UV/Vis/NIR spectrophotometry, and their redox reactions were investigated by cyclic voltammetry. We found that the major ions of uranium species dissolved in the melt were uranyl penta-valent. After purging dry oxygen gas into the melt, pentavalent species were oxidized to the uranyl hexa-valent. In the cyclic voltammetry of the melt without uranium species, it was confirmed that the lithium-sodium molybdenum oxide compounds were deposited on the working electrode at the negative potential and the lithium molybdenum oxide compounds were deposited on the counter electrode at positive potential. When UO 2 was dissolved into the melt, the reductive reaction of the uranium species was observed at the reductive potential of the pure melt. This suggests that the uranium species dissolved in the melts could be recovered as mixed uranium-molybdenum oxides by electrolysis. (orig.)

  6. Proposal for an experiment at the SIN: contribution on πE3-beam dosimetry. Measurement of particle spectra after pion absorption in biologically interesting nuclei

    International Nuclear Information System (INIS)

    Appel, H.; Boehmer, V.; Bueche, G.; Kluge, W.; Matthay, H.

    It is proposed to measure the energy spectra of light charged particles (protons, deuterons, tritons, 3 He- and 4 He-nuclei) and of neutrons, after the absorption of stopped pions in the biologically interesting hydrogen, oxygen, carbon, and nitrogen nuclei. In addition, the relative particle yield will be examined in tissue-like targets such as polyethylene, plexiglas, and water. Furthermore, it is proposed to measure the coincidence spectra of two particles emitted after absorption, as a function of the angle between their impulses. In the case of a pure three-body decay, these examinations may open the possibility of drawing conclusions about the heavy recoil nuclei arising during pion absorption. Particle energy and type will be determined by a combined time-of-flight/energy measurement with totally absorbent NaI or plastic detectors. The HF signal will serve as a start signal for time-of-flight measurements

  7. Automatic reduction of large X-ray fluorescence data-sets applied to XAS and mapping experiments

    International Nuclear Information System (INIS)

    Martin Montoya, Ligia Andrea

    2017-02-01

    In this thesis two automatic methods for the reduction of large fluorescence data sets are presented. The first method is proposed in the framework of BioXAS experiments. The challenge of this experiment is to deal with samples in ultra dilute concentrations where the signal-to-background ratio is low. The experiment is performed in fluorescence mode X-ray absorption spectroscopy with a 100 pixel high-purity Ge detector. The first step consists on reducing 100 fluorescence spectra into one. In this step, outliers are identified by means of the shot noise. Furthermore, a fitting routine which model includes Gaussian functions for the fluorescence lines and exponentially modified Gaussian (EMG) functions for the scattering lines (with long tails at lower energies) is proposed to extract the line of interest from the fluorescence spectrum. Additionally, the fitting model has an EMG function for each scattering line (elastic and inelastic) at incident energies where they start to be discerned. At these energies, the data reduction is done per detector column to include the angular dependence of scattering. In the second part of this thesis, an automatic method for texts separation on palimpsests is presented. Scanning X-ray fluorescence is performed on the parchment, where a spectrum per scanned point is collected. Within this method, each spectrum is treated as a vector forming a basis which is to be transformed so that the basis vectors are the spectra of each ink. Principal Component Analysis is employed as an initial guess of the seek basis. This basis is further transformed by means of an optimization routine that maximizes the contrast and minimizes the non-negative entries in the spectra. The method is tested on original and self made palimpsests.

  8. How to calculate linear absorption spectra with lifetime broadening using fewest switches surface hopping trajectories: A simple generalization of ground-state Kubo theory

    International Nuclear Information System (INIS)

    Petit, Andrew S.; Subotnik, Joseph E.

    2014-01-01

    In this paper, we develop a surface hopping approach for calculating linear absorption spectra using ensembles of classical trajectories propagated on both the ground and excited potential energy surfaces. We demonstrate that our method allows the dipole-dipole correlation function to be determined exactly for the model problem of two shifted, uncoupled harmonic potentials with the same harmonic frequency. For systems where nonadiabatic dynamics and electronic relaxation are present, preliminary results show that our method produces spectra in better agreement with the results of exact quantum dynamics calculations than spectra obtained using the standard ground-state Kubo formalism. As such, our proposed surface hopping approach should find immediate use for modeling condensed phase spectra, especially for expensive calculations using ab initio potential energy surfaces

  9. Above band gap absorption spectra of the arsenic antisite defect in low temperature grown GaAs and AlGaAs

    DEFF Research Database (Denmark)

    Dankowski, S. U.; Streb, D.; Ruff, M.

    1996-01-01

    coefficients at the band gap are twice as high as for high temperature grown materials. By annealing the samples, we obtained a drastic reduced absorption coefficient below as well as above the band gap. We observed absorption changes up to 17 000 cm(-1) for LT-GaAs and 9000 cm(-1) for LT-AlGaAs taking place......Room temperature absorption spectra of low temperature molecular beam epitaxy grown GaAs (LT-GaAs) and AlGaAs (LT-AlGaAs) are reported. We performed measurements in an extended spectral range from 0.8 eV to photon energies of 2.8 eV far above the band gap. For as-grown LT-materials, the absorption...

  10. Photoluminescence and optical absorption spectra of {gamma}{sub 1}-(Ga{sub x}In{sub 1-x}){sub 2}Se{sub 3} mixed crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kranjcec, M. [Department of Geotechnics, University of Zagreb, 7 Hallerova Aleja, Varazdin, 42000 (Croatia); Ruder Boskovic Institute, 54 Bijenicka Cesta, Zagreb, 10000 (Croatia); Studenyak, I.P. [Uzhhorod National University, 46 Pidhirna Str., Uzhhorod, 88000 (Ukraine); Azhniuk, Yu. M. [Institute of Electron Physics, Ukr. Nat. Acad. Sci., 21 Universytetska Str., Uzhhorod, 88000 (Ukraine)

    2005-08-01

    Temperature and compositional studies of photoluminescence and optical absorption edge spectra of {gamma}{sub 1}-(Ga{sub x}In{sub 1-x}){sub 2}Se{sub 3} mixed crystals with x=0.1-0.4 are performed. Exciton and impurity-related photoluminescence bands are revealed at low temperatures and Urbach shape of the absorption edge is observed in the temperature range 77-300 K. Temperature and compositional dependences of the photoluminescence band spectral positions and halfwidths as well as optical pseudogap and absorption edge energy width are investigated. Mechanisms of radiative recombination and optical absorption as well as crystal lattice disordering processes in {gamma}{sub 1}-(Ga{sub x}In{sub 1-x}){sub 2}Se{sub 3} solid solutions are studied. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. X-ray absorption spectroscopy and high-energy XRD study of the local environment of copper in antibacterial copper-releasing degradable phosphate glasses

    OpenAIRE

    Pickup, David M.; Ahmed, Ifty; Fitzgerald, Victoria; Moss, Rob M.; Wetherall, Karen; Knowles, Jonathan C.; Smith, Mark E.; Newport, Robert J.

    2006-01-01

    Phosphate-based glasses of the general formula Na2O-CaO-P2O5 are degradable in an aqueous environment, and therefore can act as antibacterial materials through the inclusion of ions such as copper. In this study, CuO and Cu2O were added to Na2O-CaO-P2O5 glasses (1-20 mol% Cu) and X-ray absorption spectroscopy (XAS) and high-energy X-ray diffraction (HEXRD) used to probe the local environment of the copper ions. Copper K-edge X-ray absorption near-edge structure (XANES) spectra confirm the oxi...

  12. Assignment of near-edge x-ray absorption fine structure spectra of metalloporphyrins by means of time-dependent density-functional calculations

    International Nuclear Information System (INIS)

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-01-01

    The C 1s and N 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of three prototype tetraphenyl porphyrin (TPP) molecules are discussed in the framework of a combined experimental and theoretical study. We employ time-dependent density-functional theory (TDDFT) to compute the NEXAFS spectra of the open- and closed-shell metalloporphyrins CoTPP and ZnTPP as well as the free-base 2HTPP in realistic nonplanar conformations. Using Becke's well-known half-and-half hybrid functional, the computed core excitation spectra are mostly in good agreement with the experimental data in the low-energy region below the appropriate ionization threshold. To make these calculations feasible, we apply a new, simple scheme based on TDDFT using a modified single-particle input spectrum. This scheme is very easy to implement in standard codes and allows one to compute core excitation spectra at a similar cost as ordinary UV/vis spectra even for larger molecules. We employ these calculations for a detailed assignment of the NEXAFS spectra including subtle shifts in certain peaks of the N 1s spectra, which depend on the central coordination of the TPP ligand. We furthermore assign the observed NEXAFS resonances to the individual molecular subunits of the investigated TPP molecules.

  13. UV-VIS absorption spectra of molten AgCl and AgBr and of their mixtures with group I and II halide salts

    Energy Technology Data Exchange (ETDEWEB)

    Greening, Giorgio G.W. [Technische Universitaet Darmstadt (Germany). Eduard-Zintl-Institut fuer Anorganische und Physikalische Chemie

    2015-07-01

    The UV-VIS absorption spectra of (Ag{sub 1-X}[Li-Cs, Ba]{sub X})Cl and of (Ag{sub 1-X}[Na, K, Cs]{sub X})Br at 823 K at the concentrations X=0.0, 0.1, 0.2 have been measured. The findings show that on adding the respective halides to molten silver chloride and silver bromide, shifts of the fundamental absorption edge to shorter wavelengths result. A correlation between the observed shifts and the expansion of the silver sub-lattice is found, which is valid for both silver halide systems studied in this work.

  14. Influence of Gamma-Ray Irradiation on Absorption and Fluorescent Spectra of Nd:YAG and Yb:YAG Laser Crystals

    Institute of Scientific and Technical Information of China (English)

    SUN Dun-Lu; ZHANG Qing-Li; XIAO Jing-Zhong; LUO Jian-Qiao; JIANG Hai-He; YIN Shao-Tang

    2008-01-01

    We investigate the influence of gamma-ray irradiation on the absorption and fluorescent spectra of Nd3+ : Y3Al5O12 (Nd:YAG) and Yb3+ :Y3Al5O12 (Yb:YAG) crystals grown by the Czochralski method. Two additional absorption (AA) bands induced by gamma-ray irradiation appear at 255nm and 340nm. The former is eontributed due to Fe3+ impurity, the latter is due to Fe2+ ions and F-type colour centres. The intensity of the excitation and emission spectra as well as the fluorescent lifetime of Nd:YAG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, the same dose irradiation does not impair the fluorescent properties of Yb: YA G crystal. These results indicate that Yb: YA G crystal possesses the advantage over Nd: YA G crystal that has better reliability for applications in harsh radiant environment.

  15. Synthesis and investigation of solvent effects on the ultraviolet absorption spectra of 5-substituted-4-methyl-3-cyano-6-hydroxy-2-pyridones

    Directory of Open Access Journals (Sweden)

    NATASA V. VALENTIC

    2001-08-01

    Full Text Available A number of 5-substituted-4-methyl-3-cyano-6-hydroxy-2-pyridones from cyanoacetamide and the corresponding alkyl ethyl acetoacetates were synthesized according to modified literature procedures. The alkyl ethyl acetoacetates were obtained by the reaction of C-alkylation of ethyl acetoacetate. An investigation of the reaction conditions for the synthesis of 4-methyl-3-cyano-6-hydroxy-2-pyridone from cyanoacetamide and ethyl acetoacetate in eight different solvents was also performed. The ultraviolet absorption spectra of synthesized pyridones were measured in nine different solvents in the range 200–400 nm. The effects of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of linear solvation energy relationships using a general equation of the form n = n0 + sp* + aa + bb, where p* is a measure of the solvent polarity, a is the scale of the solvent hydrogen bond donor acidities and b is the scale of the solvent hydrogen bond acceptor basicities.

  16. Studies on pigments of the myxomycete Physarum nudum. I. Absorption spectra of the crude extracts of pigments from plasmodia cultured in continuous light and in darkness

    Directory of Open Access Journals (Sweden)

    L. Rakoczy

    2015-01-01

    Full Text Available 1. Method for extraction and crude separation of the plasmodial pigments of the myxomycete Physarum nudum cultured in light and in darkness were elaborated. 2.\tBy the use of various solvents in the procedure of extraction three pigment fractions were obtained from plasmodia cultured in the dark and four fractions from those grown under continuous light. 3. The absorption spectra of the particular fractions within the UV and visible range were determined.

  17. Artifact suppression in electron paramagnetic resonance imaging of 14N- and 15N-labeled nitroxyl radicals with asymmetric absorption spectra

    Science.gov (United States)

    Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

    2014-10-01

    This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.

  18. Determining CDOM Absorption Spectra in Diverse Coastal Environments Using a Multiple Pathlength, Liquid Core Waveguide System. Measuring the Absorption of CDOM in the Field Using a Multiple Pathlength Liquid Waveguide System

    Science.gov (United States)

    Miller, Richard L.; Belz, Mathias; DelCastillo, Carlos; Trzaska, Rick

    2000-01-01

    We evaluated the accuracy, sensitivity and precision of a multiple pathlength, liquid core waveguide (MPLCW) system for measuring colored dissolved organic matter (CDOM) absorption in the UV-visible spectral range (370-700 nm). The MPLCW has four optical paths (2.0, 9.8, 49.3, and 204 cm) coupled to a single Teflon AF sample cell. Water samples were obtained from inland, coastal and ocean waters ranging in salinity from 0 to 36 PSU. Reference solutions for the MPLCW were made having a refractive index of the sample. CDOM absorption coefficients, a(sub CDOM), and the slope of the log-linearized absorption spectra, S, were compared with values obtained using a dual-beam spectrophotometer. Absorption of phenol red secondary standards measured by the MPLCW at 558 nm were highly correlated with spectrophotometer values (r > 0.99) and showed a linear response across all four pathlengths. Values of a(sub CDOM) measured using the MPLCW were virtually identical to spectrophotometer values over a wide range of concentrations. The dynamic range of a(sub CDOM) for MPLCW measurements was 0.002 - 231.5/m. At low CDOM concentrations (a(sub 370) CDOM) were slightly greater than MPLCW values and showed larger fluctuations at longer wavelengths due to limitations in instrument precision. In contrast, MPLCW spectra followed an exponential to 600 nm for all samples. The maximum deviation in replicate MPLCW spectra was less than 0.001 absorbance units. The portability, sampling, and optical characteristics of a MPLCW system provide significant enhancements for routine CDOM absorption measurements in a broad range of natural waters.

  19. Dispersive XAS on a High Brilliance Source: Highlights and Future Opportunities

    International Nuclear Information System (INIS)

    Pascarelli, S.; Aquilanti, G.; Guilera, G.; Mathon, O.; Newton, M. A.; Trapananti, A.; Dubrovinsky, L.; Munoz, M.; Pasquale, M.

    2007-01-01

    Energy Dispersive X-ray Absorption Spectroscopy is a now a well-established method which has been applied to a broad range of applications. Ten years from the construction of beamline ID24 at the ESRF, the first dispersive XAS spectrometer using undulator radiation on a third generation source, we report an overview of recent results in very diverse fields of research, ranging from automotive catalysts to magnetism at extreme conditions. We also illustrate how pushing the instrument to its limits has opened new opportunities, such as an enhanced sensitivity to detection of tiny atomic displacements and the potential for micro-probe redox and speciation imaging

  20. Influence of TiO2 Nanocrystals Fabricating Dye-Sensitized Solar Cell on the Absorption Spectra of N719 Sensitizer

    Directory of Open Access Journals (Sweden)

    Puhong Wen

    2012-01-01

    Full Text Available The absorption spectra of N719 sensitizer anchored on the films prepared by TiO2 nanocrystals with different morphology and size were investigated for improving the performance of dye-sensitized solar cell (DSC. We find that the morphology and size of TiO2 nanocrystals can affect the UV-vis and FT-IR spectra of the sensitizer anchored on their surfaces. In particular, the low-energy metal-to-ligand charge-transfer transitions (MLCT band in the visible absorption spectra of N719 is strongly affected, and locations of these MLCT bands revealed larger differences. The results indicate that there is a red shift of MLCT band in the spectra obtained by using TiO2 nanocrystals with long morphology and large size compared to that in solution. And it produced a larger red-shift on the MLCT band after TiO2 nanocrystals with small size mixed with some long nanocrystals. Accordingly, the utilization rate to visible light is increased. This is a reason why the DSC prepared by using such film as a photoelectrode has better performance than before mixing.

  1. Effect of ligand nature and geometry of its surrounding on electron absorption spectra of NpO22+ and PuO22+ compounds

    International Nuclear Information System (INIS)

    Sokolov, E.I.; Tebelev, L.G.; Melkaya, R.F.; Rykov, A.G.

    1981-01-01

    Electron absorption spectra of actinide compounds with the symmetry of the nearest surrounding of actinyl-ions as follows: Dsub(2h)-AnO 2 (NO 3 ) 2 xnH 2 O, AnO 2 (CH 3 COO) 2 x2H 2 O; Dsub(3h)-MAnO 2 (NO 3 ) 3 (M-K, Rb, Cs), NaAnO 2 (CH 3 COO) 3 , (NH 4 ) 4 AnO 2 (CO 3 ) 3 ; Dsub(4h)-Cs 2 AnO 2 Cl 4 , where An-U, Np, Pb, are measured at room temperature. It is established that position, intensity and form of absorption bands in neptunyl compound spectra are sensible equally to geometry of coordination sphere and to ligand nature. The character of the change of plutonyl compound spectra is the same as of neptunyl ones: it is determined both by surrounding geometry and chemical nature of ligands. It is shown that in the near infrared region ligand effect on plutonyl compound spectra with the symmetry of anion complex Dsub(3h) is weaker than in the visible region

  2. A solid-state NMR and DFT study of compositional modulations in AlxGa1-xAs

    NARCIS (Netherlands)

    Knijn, Paulus J.; Bentum, P. Jan M. van; Eck, Ernst R.H. van; Fang, Changming; Grimminck, Dennis L.A.G.; Groot, Robert A. de; Havenith, Remco W.A.; Marsman, Martijn; Meerts, W. Leo; Wijs, Gilles A. de; Kentgens, Arno P.M.

    2010-01-01

    We have conducted 75As and 69Ga Nuclear Magnetic Resonance (NMR) experiments to investigate order/disorder in AlxGa1-xAs lift-off films with x ~ 0.297 and 0.489. We were able to identify all possible As(AlnGa4-n) sites with n = 0–4 coordinations in 75As NMR spectra using spin-echo experiments at

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

    Science.gov (United States)

    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.

  4. X-ray absorption spectroscopy study on the thermal and hydrazine reduction of graphene oxide

    International Nuclear Information System (INIS)

    Liang, Xianqing; Wang, Yu; Zheng, Huiyuan; Wu, Ziyu

    2014-01-01

    Highlights: • XAS study of GO and reduced GO was performed. • Detailed evolution of the electronic structures and chemical bonding of GO was revealed. • A new efficient route for the reduction of GO is proposed. - Abstract: X-ray absorption spectroscopy (XAS) was applied to systemically investigate the deoxygenation of graphene oxide (GO) via annealing and hydrazine treatment. Detailed evolution of the electronic structures and chemical bonding of GO was presented. The enhanced intensity of π * resonance and the appearance of splitting σ * resonance in C K-edge XAS spectra suggest high extents of recoveries of π-conjugation upon reduction using thermal annealing or hydrazine. Experimental results revealed that the carboxyl as well as epoxide and hydroxyl groups on the surface of GO were thermally reduced first, followed by the more difficult removal of carbonyl and cyclic ether groups at higher temperatures. The hydrazine reduction could remove epoxide, hydroxyl and carboxyl groups effectively, whereas the carbonyl groups were partially reduced with the incorporation of nitrogen species simultaneously. The residual oxygen functional groups on hydrazine-reduced GO could be further removed after modest thermal annealing. It was proposed that a combination of both types of reductions would give the best deoxygenation efficiency for the production of graphene

  5. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184-8588 (Japan); Fujii, Kentaro; Yokoya, Akinari [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Fukuda, Yoshihiro; Saitoh, Yuji [Synchrotron Radiation Research Center, Japan Atomic Energy Agency, Sayo-gun, Hyougo 679-5148 (Japan)

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5{sup ′}-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5{sup ′}-monophosphate, and adenosine 5{sup ′}-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  6. Infrared absorption spectra of gaseous HD. II. Collision-induced fundamental band of HD in HD--Ne and HD--Ar mixtures at room temperature

    International Nuclear Information System (INIS)

    Prasad, R.D.G.; Reddy, S.P.

    1976-01-01

    The collision-induced infrared absorption spectra of the fundamental band of HD in binary mixtures of HD with Ne and Ar at room temperature have been studied with an absorption path length of 105.2 cm for different base densities of HD in the range 8--20 amagat and a number of total gas densities up to 175 amagat. The observed features of the profiles of the enhancement of absorption in these mixtures resemble closely those of the corresponding profiles of the fundamental band of H 2 in binary mixtures with Ne and Ar. The binary absorption coefficients of the band obtained from the measured integrated intensities are (1.84 +- 0.06) x 10 -35 and (4.41 +- 0.06) x 10 -35 cm 6 s -1 for HD--Ne and HD--Ar, respectively. The characteristic half-width parameters, delta/subd/ and delta/subc/ of the overlap transitions and delta/subq/ (and delta/subq//sub prime/) of the quadrupolar transitions, are obtained from an analysis of the profiles of the enhancement of absorption in both these mixtures. The quantity delta/subc/ which is the half-width of the intercollisional interference dip of the Q branch increases with the density of the perturbing gas Ne or Ar, and for HD--Ne it varies in a manner similar to that for HD--He as described in Paper I of this series

  7. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    Energy Technology Data Exchange (ETDEWEB)

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-08

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

  8. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    International Nuclear Information System (INIS)

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-01

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings

  9. The investigation of hydrogens bonds between sulphur-bearing heterocyclic and proton-donor compounds by IR absorption spectra

    International Nuclear Information System (INIS)

    Narziev, B.N.; Nurulloev, M.; Makhkambaev, D.

    1982-01-01

    In this article the results of intermolecular interaction study of sulfur-containing heterocyclic (thiophene, thiophane) and proton-donar (water, alcohol, carbonic acids, chlorophon) molecules for measuring of IR spectrum absorption of protondonar compounds in soluted shape are presented

  10. What is the correct Fe L{sub 23} X-ray absorption spectrum of magnetite?

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaohui; Kalirai, Samanbir S. [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON L8S 4M1 (Canada); Hitchcock, Adam P., E-mail: aph@mcmaster.ca [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON L8S 4M1 (Canada); Bazylinski, Dennis A. [School of Life Sciences, University of Nevada at Las Vegas, Las Vegas, NV 89154-4004 (United States)

    2015-02-15

    Highlights: • Fe L{sub 3} X-ray absorption spectra of biological (MV-1 magnetotactic bacteria) and abiotic (Sigma–Aldrich) nano-magnetite are reported. • An inconsistency in the literature for this spectrum is documented. • Powder diffraction shows the abiotic sample is partly oxidized, toward maghemite. • H{sub 2} thermal reduction converts the Fe L{sub 3} spectrum of the abiotic sample to that of the biotic. • Strong oxidation (air, 600 °C) is needed to convert the spectrum of the biotic magnetite to that of maghemite; magnetosome chains are protected by an air-impervious membrane. - Abstract: Various groups have reported Fe L{sub 23} X-ray absorption spectra (XAS) of magnetite (Fe{sub 3}O{sub 4}), each claiming to be that of magnetite, but which contradict each other. Here we report an XAS study of two kinds of magnetite: one is biogenic magnetite nanocrystals extracted from the magnetotactic bacterium Magnetovibrio blakemorei strain MV-1; the other is synthetic, abiogenically produced nano-magnetite. We see significantly different XAS spectra of these two materials. Only when the abiogenic magnetite was reduced under H{sub 2} did it give the same spectrum as the biogenic sample. Extensive heating of the biogenic magnetite in air produced spectra similar to that of the abiogenic magnetite. These two spectra are typical of the range of published Fe L{sub 23} spectra of magnetite. X-ray diffraction confirmed that the biogenic material is stoichiometric Fe{sub 3}O{sub 4}, and showed that the as-received or partly reduced abiogenic material is a non-stoichiometric oxide, intermediate between magnetite and maghemite (γ-Fe{sub 2}O{sub 3}). When the membrane which surrounds magnetosome chains was intact, the biotic magnetite single crystals were surprisingly resistant to oxidation. This study clarifies a significant confusion existing in the literature as to the correct Fe L{sub 23} X-ray absorption spectra of magnetite and maghemite.

  11. DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state

    Science.gov (United States)

    Hanuza, J.; Godlewska, P.; Lisiecki, R.; Ryba-Romanowski, W.; Kadłubański, P.; Lorenc, J.; Łukowiak, A.; Macalik, L.; Gerasymchuk, Yu.; Legendziewicz, J.

    2018-05-01

    The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln = Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.

  12. FTIR measurements of mid-IR absorption spectra of gaseous fatty acid methyl esters at T=25–500 °C

    International Nuclear Information System (INIS)

    Campbell, M.F.; Freeman, K.G.; Davidson, D.F.; Hanson, R.K.

    2014-01-01

    Gas-phase mid-infrared (IR) absorption spectra (2500–3400 cm −1 ) for eleven fatty acid methyl esters (FAMEs) have been quantitatively measured at temperatures between 25 and 500 °C using an FTIR spectrometer with a resolution of 1 cm −1 . Using these spectra, the absorption cross section at 3.39 μm, corresponding to the monochromatic output of a helium–neon laser, is reported for each of these fuels as a function of temperature. The data indicate that the 3.39 μm cross section values of saturated FAMEs vary linearly with the logarithm of the number of C-H bonds in the molecule. - Highlights: • Infrared spectra of 11 fatty acid methyl esters (C 3 –C 11 ) have been measured. • A linear relationship for predicting 3.39 μm cross section values is proposed. • A molecule’s integrated area is linearly related to its number of C-H bonds. • Mono-unsaturation decreases cross section values

  13. Impact effects of gamma irradiation on the optical and FT infrared absorption spectra of some Nd3+-doped soda lime phosphate glasses

    Science.gov (United States)

    Marzouk, M. A.; Elkashef, I. M.; Elbatal, H. A.

    2018-04-01

    The main aim of the present work is to study by two collective optical and FTIR spectral measurements some prepared Nd2O3-doped soda lime phosphate glasses before and after gamma irradiation with dose (9 Mrad). The spectral data reveal two strong UV absorption peaks which are correlated with unavoidable trace iron impurities beside extended additional characteristic bands due to Nd3+ ions. Gamma irradiation on the undoped glass produces slight decrease of the intensity of the UV absorption and the generation of an induced visible band and these effects are controlled with two photochemical reduction of some Fe3+ ions to Fe2+ ions together with the formation of nonbridging oxygen hole center (NBOHC) or phosphorous oxygen hole center (POHC). The impact effect of gamma irradiation on the spectra of Nd2O3-doped glasses is limited due to suggested shielding behavior of neodymium ions. FT-infrared spectra show vibrational modes due to main Q2-Q3 phosphate groups and the response of gamma irradiation of the IR spectra is low and the limited variations are related to suggested changes in some bond angles and bond lengths which cause the observed decrease to the intensities of some IR bands.

  14. Electronic state of cerium-based catalysts studied by spectroscopic methods (XPS, XAS)

    International Nuclear Information System (INIS)

    Le Normand, F.; Bernhardt, P.; Hilaire, L.; Kili, K.; Maire, G.; Krill, G.

    1987-01-01

    X-ray Photoelectron Spectroscopy (XPS) of the 3d core level of cerium and X-ray Absorption Spectroscopy (XAS) of the L III absorption edge of cerium have been used to study Pd/CeO 2 , Pd-Ce/γAl 2 O 3 and Ce/γAl 2 O 3 catalysts. The oxidation state of cerium was found to decrease with decreasing amounts of cerium on the surface. It was quite close to III for very low contents of cerium (2-3%). For higher cerium contents the oxidation state was nearer to IV but differences between the two methods were found, owing to the fact that XAS is a volume sensitive probe. The oxidation state of cerium was also lower for Pd-Ce/γAl 2 O 3 than for Ce/γAl 2 O 3 , suggesting the formation of Ce III OCl, chlorine coming from the precursor salt of palladium. 15 refs.; 5 figs.; 1 table

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

    Science.gov (United States)

    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.

  16. Application of Time-Dependent Density Functional and Natural Bond Orbital Theories to the UV-vis Absorption Spectra of Some Phenolic Compounds.

    Science.gov (United States)

    Marković, Svetlana; Tošović, Jelena

    2015-09-03

    The UV-vis properties of 22 natural phenolic compounds, comprising anthraquinones, neoflavonoids, and flavonoids were systematically examined. The time-dependent density functional theory (TDDFT) approach in combination with the B3LYP, B3LYP-D2, B3P86, and M06-2X functionals was used to simulate the UV-vis spectra of the investigated compounds. It was shown that all methods exhibit very good (B3LYP slightly better) performance in reproducing the examined UV-vis spectra. However, the shapes of the Kohn-Sham molecular orbitals (MOs) involved in electronic transitions were misleading in constructing the MO correlation diagrams. To provide better understanding of redistribution of electron density upon excitation, the natural bond orbital (NBO) analysis was applied. Bearing in mind the spatial and energetic separations, as well as the character of the π bonding, lone pair, and π* antibonding natural localized molecular orbitals (NLMOs), the "NLMO clusters" were constructed. NLMO cluster should be understood as a part of a molecule characterized with distinguished electron density. It was shown that all absorption bands including all electronic transitions need to be inspected to fully understand the UV-vis spectrum of a certain compound, and, thus, to learn more about its UV-vis light absorption. Our investigation showed that the TDDFT and NBO theories are complementary, as the results from the two approaches can be combined to interpret the UV-vis spectra. Agreement between the predictions of the TDDFT approach and those based on the NLMO clusters is excellent in the case of major electronic transitions and long wavelengths. It should be emphasized that the approach for investigation of UV-vis light absorption based on the NLMO clusters is applied for the first time.

  17. Multiconfigurational and DFT analyses of the electromeric formulation and UV-vis absorption spectra of the superoxide adduct of ferrous superoxide reductase.

    Science.gov (United States)

    Attia, Amr A A; Cioloboc, Daniela; Lupan, Alexandru; Silaghi-Dumitrescu, Radu

    2016-12-01

    The putative initial adduct of ferrous superoxide reductase (SOR) with superoxide has been alternatively formulated as ferric-peroxo or ferrous-superoxo. The ~600-nm UV-vis absorption band proposed to be assigned to this adduct (either as sole intermediate in the SOR catalytic cycle, or as one of the two intermediates) has recently been interpreted as due to a ligand-to-metal charge transfer, involving thiolate and superoxide in a ferrous complex, contrary to an alternative assignment as a predominantly cysteine thiolate-to-ferric charge transfer in a ferric-peroxo electromer. In an attempt to clarify the electromeric formulation of this adduct, we report a computational study using a multiconfigurational complete active space self-consistent field (MC-CASSCF) wave function approach as well as modelling the UV-vis absorption spectra with time-dependent density functional theory (TD-DFT). The MC-CASSCF calculations disclose a weak interaction between iron and the dioxygenic ligand and a dominant configuration with an essentially ferrous-superoxo character. The computed UV-vis absorption spectra reveal a marked dependence on the choice of density functional - both in terms of location of bands and in terms of orbital contributors. For the main band in the visible region, besides the recently reported thiolate-to-superoxide charge transfer, a more salient, and less functional-dependent, feature is a thiolate-to-ferric iron charge transfer, consistent with a ferric-peroxo electromer. By contrast, the computed UV-vis spectra of a ferric-hydroperoxo SOR model match distinctly better (and with no qualitative dependence on the DFT methodology) the 600-nm band as due to a mainly thiolate-to-ferric character - supporting the assignment of the SOR "600-nm intermediate" as a S=5/2 ferric-hydroperoxo species. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. Absorption spectra of CsNd(MoO4)2 and CsGd(MoO4)2-Nd3+ crystals in strong magnetic fields

    International Nuclear Information System (INIS)

    Gorban', I.S.; Kozeeva, L.P.; Slobodyanyuk, A.V.; Shevchenko, V.A.

    1987-01-01

    The comparison of the electronic structure of Nd 3+ in CsNd(MoO 4 ) 2 and CsGd(MoO 4 ) 2 - Nd 3+ crystals is made. It is established that in these crystals the activator centers, mainly, of the certain type with the symmetry of the local environment C 2 are formed. The absorption spectra of self-activated CsNd(MoO 4 ) 2 crystal differ from spectra of CsGd(MoO 4 ) 2 - Nd 3+ by the presence of the vibrating structure. The Stark splittings of energy levels of Nd 3+ in the investigated crystalline matrices are more sensitive to the environment effect than the Zeeman ones. The ground state of Nd 3+ ion in CsNd(MoO 4 ) 2 and CsGd(MoO 4 ) 2 molybdates is characterized by the similar values of g-factors

  19. Calculated Hanle transmission and absorption spectra of the 87Rb D1 line with residual magnetic field for arbitrarily polarized light

    International Nuclear Information System (INIS)

    Noh, Heung-Ryoul; Moon, Han Seb

    2010-01-01

    This paper reports a theoretical study on the transmission spectra of an arbitrarily polarized laser beam through a rubidium cell with or without a buffer gas in Hanle-type coherent population trapping (CPT). This study examined how laser polarization, transverse magnetic field, and collisions with buffer gas affects the spectrum. The transmission spectrum due to CPT and the absorption spectrum due to the level crossing absorption (LCA) were calculated according to the laser polarization. The results show that the LCA is strongly dependent on the transverse magnetic field and interaction time of the atoms with a laser light via collisions with the buffer gas. In addition, the spectral shape of the calculated Hanle spectrum is closely related to the direction between the (stray) transverse magnetic field and polarization of the laser.

  20. Use of Isobestic and Isoemission Points in Absorption and Luminescence Spectra for Study of the Transformation of Radiation Defects in Lithium Fluoride

    Science.gov (United States)

    Voitovich, A. P.; Kalinov, V. S.; Stupak, A. P.; Runets, L. P.

    2015-03-01

    Isobestic and isoemission points are recorded in the combined absorption and luminescence spectra of two types of radiation defects involved in complex processes consisting of several simultaneous parallel and sequential reactions. These points are observed if a constant sum of two terms, each formed by the product of the concentration of the corresponding defect and a characteristic integral coefficient associated with it, is conserved. The complicated processes involved in the transformation of radiation defects in lithium fluoride are studied using these points. It is found that the ratio of the changes in the concentrations of one of the components and the reaction product remains constant in the course of several simultaneous reactions.

  1. The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

    Science.gov (United States)

    Halasinski, Thomas M.; Hudgins, Douglas M.; Salama, Farid; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

    1999-01-01

    The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

  2. First-principles calculation of optical absorption spectra in conjugated polymers: Role of electron-hole interaction

    International Nuclear Information System (INIS)

    Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.

    2000-01-01

    Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV)

  3. First-principles calculation of optical absorption spectra in conjugated polymers: Role of electron-hole interaction

    Energy Technology Data Exchange (ETDEWEB)

    Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.

    2000-03-20

    Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV).

  4. Molecular dynamics simulation and TDDFT study of the structures and UV-vis absorption spectra of MCT-β-CD and its inclusion complexes.

    Science.gov (United States)

    Lu, Huijuan; Wang, Yujiao; Xie, Xiaomei; Chen, Feifei; Li, Wei

    2015-01-01

    In this research, the inclusion ratios and inclusion constants of MCT-β-CD/PERM and MCT-β-CD/CYPERM inclusion complexes were measured by UV-vis and fluorescence spectroscopy. The inclusion ratios are both 1:1, and the inclusion constants are 60 and 342.5 for MCT-β-CD/PERM and MCT-β-CD/CYPERM, respectively. The stabilities of inclusion complexes were investigated by MD simulation. MD shows that VDW energy plays a vital role in the stability of inclusion complex, and the destruction of inclusion complex is due to the increasing temperature. The UV-vis absorption spectra of MCT-β-CD and its inclusion complexes were studied by time-dependent density functional theory (TDDFT) method employing BLYP-D3, B3LYP-D3 and M06-2X-D3 functionals. BLYP-D3 well reproduces the UV-vis absorption spectrum and reveals that the absorption bands of MCT-β-CD mainly arise from n→π(∗) and n→σ(∗) transition, and those of inclusion complexes mainly arise from intramolecular charge transfer (ICT). ICT results in the shift of main absorption bands of MCT-β-CD. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Optical Absorption Spectra and Electronic Properties of Symmetric and Asymmetric Squaraine Dyes for Use in DSSC Solar Cells: DFT and TD-DFT Studies

    Directory of Open Access Journals (Sweden)

    Reda M. El-Shishtawy

    2016-04-01

    Full Text Available The electronic absorption spectra, ground-state geometries and electronic structures of symmetric and asymmetric squaraine dyes (SQD1–SQD4 were investigated using density functional theory (DFT and time-dependent (TD-DFT density functional theory at the B3LYP/6-311++G** level. The calculated ground-state geometries reveal pronounced conjugation in these dyes. Long-range corrected time dependent density functionals Perdew, Burke and Ernzerhof (PBE, PBE1PBE (PBE0, and the exchange functional of Tao, Perdew, Staroverov, and Scuseria (TPSSh with 6-311++G** basis set were employed to examine optical absorption properties. In an extensive comparison between the optical data and DFT benchmark calculations, the BEP functional with 6-311++G** basis set was found to be the most appropriate in describing the electronic absorption spectra. The calculated energy values of lowest unoccupied molecular orbitals (LUMO were 3.41, 3.19, 3.38 and 3.23 eV for SQD1, SQD2, SQD3, and SQD4, respectively. These values lie above the LUMO energy (−4.26 eV of the conduction band of TiO2 nanoparticles indicating possible electron injection from the excited dyes to the conduction band of the TiO2 in dye-sensitized solar cells (DSSCs. Also, aromaticity computation for these dyes are in good agreement with the data obtained optically and geometrically with SQD4 as the highest aromatic structure. Based on the optimized molecular geometries, relative positions of the frontier orbitals, and the absorption maxima, we propose that these dyes are suitable components of photovoltaic DSSC devices.

  6. XAS Studies of Arsenic in the Environment

    International Nuclear Information System (INIS)

    Charnock, J. M.; Polya, D. A.; Gault, A. G.; Morgan, A. J.

    2007-01-01

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

  7. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, W. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Chu, W.S.; Yang, F.F.; Yu, M.J.; Chen, D.L.; Guo, X.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhou, D.W.; Shi, N. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Niu, L.W.; Teng, M.K. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Gong, W.M. [Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Benfatto, M. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Wu, Z.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy)], E-mail: wuzy@ihep.ac.cn

    2007-09-21

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase (LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  8. Quantitative investigation of two metallohydrolases by X-ray absorption spectroscopy near-edge spectroscopy

    International Nuclear Information System (INIS)

    Zhao, W.; Chu, W.S.; Yang, F.F.; Yu, M.J.; Chen, D.L.; Guo, X.Y.; Zhou, D.W.; Shi, N.; Marcelli, A.; Niu, L.W.; Teng, M.K.; Gong, W.M.; Benfatto, M.; Wu, Z.Y.

    2007-01-01

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase (LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations

  9. CONFIRMATION OF ENHANCED DWARF-SENSITIVE ABSORPTION FEATURES IN THE SPECTRA OF MASSIVE ELLIPTICAL GALAXIES: FURTHER EVIDENCE FOR A NON-UNIVERSAL INITIAL MASS FUNCTION

    International Nuclear Information System (INIS)

    Van Dokkum, Pieter G.; Conroy, Charlie

    2011-01-01

    We recently found that massive cluster elliptical galaxies have strong Na I λ8183, 8195 and FeH λ9916 Wing-Ford band absorption, indicating the presence of a very large population of stars with masses ∼ sun . Here we test this result by comparing the elliptical galaxy spectra to those of luminous globular clusters associated with M31. These globular clusters have similar metallicities, abundance ratios, and ages as massive elliptical galaxies but their low dynamical mass-to-light ratios rule out steep stellar initial mass functions (IMFs). From high-quality Keck spectra we find that the dwarf-sensitive absorption lines in globular clusters are significantly weaker than in elliptical galaxies and consistent with normal IMFs. The differences in the Na I and Wing-Ford indices are 0.027 ± 0.007 mag and 0.017 ± 0.006 mag, respectively. We directly compare the two classes of objects by subtracting the averaged globular cluster spectrum from the averaged elliptical galaxy spectrum. The difference spectrum is well fit by the difference between a stellar population synthesis model with a bottom-heavy IMF and one with a bottom-light IMF. We speculate that the slope of the IMF may vary with velocity dispersion, although it is not yet clear what physical mechanism would be responsible for such a relation.

  10. First-principles calculations of K-shell X-ray absorption spectra for warm dense nitrogen

    International Nuclear Information System (INIS)

    Li, Zi; Zhang, Shen; Kang, Wei; Wang, Cong; Zhang, Ping

    2016-01-01

    X-ray absorption spectrum is a powerful tool for atomic structure detection on warm dense matter. Here, we perform first-principles molecular dynamics and X-ray absorption spectrum calculations on warm dense nitrogen along a Hugoniot curve. From the molecular dynamics trajectory, the detailed atomic structures are examined for each thermodynamical condition. The K-shell X-ray absorption spectrum is calculated, and its changes with temperature and pressure along the Hugoniot curve are discussed. The warm dense nitrogen systems may contain isolated nitrogen atoms, N 2 molecules, and nitrogen clusters, which show quite different contributions to the total X-ray spectrum due to their different electron density of states. The changes of X-ray spectrum along the Hugoniot curve are caused by the different nitrogen structures induced by the temperature and the pressure. Some clear signatures on X-ray spectrum for different thermodynamical conditions are pointed out, which may provide useful data for future X-ray experiments.

  11. Carbon X-ray absorption spectra of fluoroethenes and acetone: a study at the coupled cluster, density functional, and static-exchange levels of theory.

    Science.gov (United States)

    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

  12. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra.

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-05

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pK a '. The determination of pK a ' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pK a =7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of -1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra

    Science.gov (United States)

    Shimada, Toru; Hasegawa, Takeshi

    2017-10-01

    The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa‧. The determination of pKa‧ is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of - 1 and the blue form that of - 2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed.

  14. Absorption spectra of localized surface plasmon resonance observed in an inline/picoliter spectrometer cell fabricated by a near ultraviolet femtosecond laser

    Science.gov (United States)

    Shiraishi, Masahiko; Nishiyama, Michiko; Watanabe, Kazuhiro; Kubodera, Shoichi

    2018-03-01

    Absorption spectra based on localized surface plasmon resonance (LSPR) were obtained with an inline/picoliter spectrometer cell. The spectrometer cell was fabricated into an optical glass fiber by focusing a near UV (NUV) femtosecond laser pulses at a wavelength of 400 nm with an energy of 30 μJ. The laser beam was focused from two directions opposite to each other to fabricate a through-hole spectrometer cell. A diameter of the cell was approximately 3 μm, and the length was approximately 62.5 μm, which was nearly equal to the core diameter of the optical fiber. Liquid solution of gold nanoparticles (GNPs) with a diameter of 5-10 nm was injected into the spectrometer cell with its volume of 0.4 pL. The absorption peak centered at 518 nm was observed. An increase of absorption associated with the increase of the number of nanoparticles was in agreement with the numerical calculation based on the Lambert-Beer law.

  15. Comparative analysis of the vibrational structure of the absorption spectra of acrolein in the excited ( S 1) electronic state

    Science.gov (United States)

    Koroleva, L. A.; Tyulin, V. I.; Matveev, V. K.; Pentin, Yu. A.

    2012-04-01

    The assignments of absorption bands of the vibrational structure of the UV spectrum are compared with the assignments of bands obtained by the CRDS method in a supersonic jet from the time of laser radiation damping for the trans isomer of acrolein in the excited ( S 1) electronic state. The ν00 trans = 25861 cm-1 values and fundamental frequencies, including torsional vibration frequency, obtained by the two methods were found to coincide in the excited electronic state ( S 1) for this isomer. The assignments of several absorption bands of the vibrational structure of the spectrum obtained by the CRDS method were changed. Changes in the assignment of (0-v') transition bands of the torsional vibration of the trans isomer in the Deslandres table from the ν00 trans trans origin allowed the table to be extended to high quantum numbers v'. The torsional vibration frequencies up to v' = 5 were found to be close to the frequencies found by analyzing the vibrational structure of the UV spectrum and calculated quantum-mechanically. The coincidence of the barrier to internal rotation (the cis-trans transition) in the one-dimensional model with that calculated quantum-mechanically using the two-dimensional model corresponds to a planar structure of the acrolein molecule in the excited ( S 1) electronic state.

  16. Phase-dependent absorption features in X-ray spectra of X-ray Dim Isolated Neutron Stars

    Science.gov (United States)

    Borghese, A.; Rea, N.; Coti Zelati, F.; Turolla, R.; Tiengo, A.; Zane, S.

    2017-12-01

    A detailed phase-resolved spectroscopy of archival XMM-Newton observations of X-ray Dim Isolated Neutron Stars (XDINSs) led to the discovery of narrow and strongly phase-dependent absorption features in two of these sources. The first was discovered in the X-ray spectrum of RX J0720.4-3125, followed by a new possible candidate in RX J1308.6+2127. Both spectral lines have similar properties: they are detected for only ˜ 20% of the rotational cycle and appear to be stable over the timespan covered by the observations. We performed Monte Carlo simulations to test the significance of these phase-variable features and in both cases the outcome has confirmed the detection with a confidence level > 4.6σ. Because of the narrow width and the strong dependence on the pulsar rotational phase, the most likely interpretation for these spectral features is in terms of resonant proton cyclotron absorption scattering in a confined high-B structure close to the stellar surface. Within the framework of this interpretation, our results provide evidence for deviations from a pure dipole magnetic field on small scales for highly magnetized neutron stars and support the proposed scenario of XDINSs being aged magnetars, with a strong non-dipolar crustal B-field component.

  17. Spectroscopic studies of the size effects in the absorption spectra of (NH2(C2H5)2)2CuCl4 nanocrystals incorporated into the PMMA photopolymer matrix

    International Nuclear Information System (INIS)

    Kapustianyk, V.; Partyka, M.; Rudyk, V.; Piasecki, M.; Brik, M.G.; Tkaczyk, S.; Ozga, K.; Plucinski, K.; Romanyshyn, S.; Kityk, I.V.

    2010-01-01

    The absorption spectra of (NH 2 (C 2 H 5 ) 2 ) 2 CuCl 4 (DEACC) single crystals and nanocrystals (NC) incorporated into the polymethyl methacrylate (PMMA) polymer matrices were investigated both experimentally and theoretically. It was established that the crystal field spectra of Cu 2+ ion detect clearly the quantum size effects. The observed spectra were analyzed using first principle crystal field quantum chemical calculations. It was shown that incorporation of NCs into the polymer matrix allows to identify the charge-transfer (CT) bands in the spectra of DEACC crystals.

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

    Science.gov (United States)

    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.

  19. In situ XAS of the solvothermal decomposition of dithiocarbamate complexes

    NARCIS (Netherlands)

    Islam, H.-U.; Roffey, A.; Hollingsworth, N.; Catlow, R.; Wolthers, M.; de Leeuw, N.H.; Bras, W.; Sankar, G.; Hogarth, G.

    2012-01-01

    An in situ XAS study of the solvothermal decomposition of iron and nickel dithiocarbamate complexes was performed in order to gain understanding of the decomposition mechanisms. This work has given insight into the steps involved in the decomposition, showing variation in reaction pathways between

  20. [The effect of electromagnetic waves of very high frequency of molecular spectra of radiation and absorption of nitric oxide on the functional activity of platelets].

    Science.gov (United States)

    Kirichuk, V F; Maĭborodin, A V; Volin, M V; Krenitskiĭ, A P; Tupikin, V D

    2001-01-01

    A study was made of the effect of electromagnetic EMI MMD-fluctuation on the frequencies of molecular spectra of radiation, and nitric oxide absorption under in vitro conditions on the functional activity of platelets in patients with unstable angina pectoris, with the help of a specially created generator. At amplitude-modulated and continuous modes of EMI MMD-irradiation of platelet-rich plasma for 5, 15 and 30 min the platelet functional activity decreases, which was shown up in reduction of their activation and fall of aggregative ability. The degree, to which platelet functional activity was inhibited, depended on the mode of irradiation and on duration of EMI MMD effect. The most obvious changes in platelet activation and in their readiness to aggregative response were observed at a continuous mode of irradiation within a 15 min interval.

  1. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

    International Nuclear Information System (INIS)

    Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

    2010-01-01

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  2. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion.

    Science.gov (United States)

    Ma, Jian; Moix, Jeremy; Cao, Jianshu

    2015-03-07

    We develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both real and imaginary time. This perturbative treatment gives a reliable absorption spectrum, where the bath is Gaussian and only the real-time expansion is involved. For the emission spectrum, the initial state is an entangled state of the system plus bath. Traditional perturbative methods are problematic when the excitations are delocalized and the energy gap is larger than the thermal energy, since the second-order expansion cannot predict the displacement of the bath. In the present method, the real-time dynamics is carried out by using the 2nd-order cumulant expansion method, while the displacement of the bath is treated more accurately by utilizing the exact reduced density matrix of the system. In a sense, the hybrid cumulant expansion is based on a generalized version of linear response theory with entangled initial states.

  3. THE VERY YOUNG TYPE Ia SUPERNOVA 2013dy: DISCOVERY, AND STRONG CARBON ABSORPTION IN EARLY-TIME SPECTRA

    International Nuclear Information System (INIS)

    Zheng, WeiKang; Filippenko, Alexei V.; Nugent, Peter E.; Graham, Melissa; Kelly, Patrick L.; Fox, Ori D.; Shivvers, Isaac; Clubb, Kelsey I.; Li, Weidong; Silverman, Jeffrey M.; Howie Marion, G.; Kasen, Daniel; Wang, Xiaofeng; Valenti, Stefano; Howell, D. Andrew; Ciabattari, Fabrizio; Cenko, S. Bradley; Balam, Dave; Hsiao, Eric; Sand, David

    2013-01-01

    The Type Ia supernova (SN Ia) 2013dy in NGC 7250 (d ≈ 13.7 Mpc) was discovered by the Lick Observatory Supernova Search. Combined with a prediscovery detection by the Italian Supernova Search Project, we are able to constrain the first-light time of SN 2013dy to be only 0.10 ± 0.05 days (2.4 ± 1.2 hr) before the first detection. This makes SN 2013dy the earliest known detection of an SN Ia. We infer an upper limit on the radius of the progenitor star of R 0 ≲ 0.25 R ☉ , consistent with that of a white dwarf. The light curve exhibits a broken power law with exponents of 0.88 and then 1.80. A spectrum taken 1.63 days after first light reveals a C II absorption line comparable in strength to Si II. This is the strongest C II feature ever detected in a normal SN Ia, suggesting that the progenitor star had significant unburned material. The C II line in SN 2013dy weakens rapidly and is undetected in a spectrum 7 days later, indicating that C II is detectable for only a very short time in some SNe Ia. SN 2013dy reached a B-band maximum of M B = –18.72 ± 0.03 mag ∼17.7 days after first light

  4. THE VERY YOUNG TYPE Ia SUPERNOVA 2013dy: DISCOVERY, AND STRONG CARBON ABSORPTION IN EARLY-TIME SPECTRA

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, WeiKang; Filippenko, Alexei V.; Nugent, Peter E.; Graham, Melissa; Kelly, Patrick L.; Fox, Ori D.; Shivvers, Isaac; Clubb, Kelsey I.; Li, Weidong [Department of Astronomy, University of California, Berkeley, CA 94720-3411 (United States); Silverman, Jeffrey M.; Howie Marion, G. [Department of Astronomy, University of Texas, Austin, TX 78712 (United States); Kasen, Daniel [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Wang, Xiaofeng [Department of Physics, Tsinghua University, Beijing 100084 (China); Valenti, Stefano; Howell, D. Andrew [Las Cumbres Observatory Global Telescope Network, 6740 Cortona Drive, Suite 102, Santa Barbara, CA 93117 (United States); Ciabattari, Fabrizio [Monte Agliale Observatory, Borgo a Mozzano, Lucca, I-55023 Italy (Italy); Cenko, S. Bradley [Astrophysics Science Division, NASA Goddard Space Flight Center, Mail Code 661, Greenbelt, MD 20771 (United States); Balam, Dave [Dominion Astrophysical Observatory, Herzberg Institute of Astrophysics, National Research Council of Canada, 5071 West Saanich Road, Victoria, BC V9E 2E7 (Canada); Hsiao, Eric [Carnegie Observatories, Las Campanas Observatory, Colina El Pino, Casilla 601 (Chile); Sand, David, E-mail: zwk@astro.berkeley.edu [Physics Department, Texas Tech University, Lubbock, TX 79409 (United States); and others

    2013-11-20

    The Type Ia supernova (SN Ia) 2013dy in NGC 7250 (d ≈ 13.7 Mpc) was discovered by the Lick Observatory Supernova Search. Combined with a prediscovery detection by the Italian Supernova Search Project, we are able to constrain the first-light time of SN 2013dy to be only 0.10 ± 0.05 days (2.4 ± 1.2 hr) before the first detection. This makes SN 2013dy the earliest known detection of an SN Ia. We infer an upper limit on the radius of the progenitor star of R {sub 0} ≲ 0.25 R {sub ☉}, consistent with that of a white dwarf. The light curve exhibits a broken power law with exponents of 0.88 and then 1.80. A spectrum taken 1.63 days after first light reveals a C II absorption line comparable in strength to Si II. This is the strongest C II feature ever detected in a normal SN Ia, suggesting that the progenitor star had significant unburned material. The C II line in SN 2013dy weakens rapidly and is undetected in a spectrum 7 days later, indicating that C II is detectable for only a very short time in some SNe Ia. SN 2013dy reached a B-band maximum of M{sub B} = –18.72 ± 0.03 mag ∼17.7 days after first light.

  5. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra.

    Science.gov (United States)

    Basavaraja, Jana; Suresh Kumar, H M; Inamdar, S R; Wari, M N

    2016-02-05

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π→π⁎ transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μ(e)). It is observed that dipole moment value of excited state (μ(e)) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state. Copyright © 2015. Published by Elsevier B.V.

  6. Diffuse Reflectance Spectroscopy of Hidden Objects, Part I: Interpretation of the Reflection-Absorption-Scattering Fractions in Near-Infrared (NIR) Spectra of Polyethylene Films.

    Science.gov (United States)

    Pomerantsev, Alexey L; Rodionova, Oxana Ye; Skvortsov, Alexej N

    2017-08-01

    Investigation of a sample covered by an interfering layer is required in many fields, e.g., for process control, biochemical analysis, and many other applications. This study is based on the analysis of spectra collected by near-infrared (NIR) diffuse reflectance spectroscopy. Each spectrum is a composition of a useful, target spectrum and a spectrum of an interfering layer. To recover the target spectrum, we suggest using a new phenomenological approach, which employs the multivariate curve resolution (MCR) method. In general terms, the problem is very complex. We start with a specific problem of analyzing a system, which consists of several layers of polyethylene (PE) film and underlayer samples with known spectral properties. To separate information originating from PE layers and the target, we modify the system versus both the number of the PE layers as well as the reflectance properties of the target sample. We consider that the interfering spectrum of the layer can be modeled using three components, which can be tentatively called transmission, absorption, and scattering contributions. The novelty of our approach is that we do not remove the reflectance and scattering effects from the spectra, but study them in detail aiming to use this information to recover the target spectrum.

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

    Science.gov (United States)

    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.

  8. Lowest excited states and optical absorption spectra of donor–acceptor copolymers for organic photovoltaics: a new picture emerging from tuned long-range corrected density functionals

    KAUST Repository

    Pandey, Laxman; Doiron, Curtis; Sears, John S.; Bré das, Jean-Luc

    2012-01-01

    Polymers with low optical gaps are of importance to the organic photovoltaics community due to their potential for harnessing a large portion of the solar energy spectrum. The combination along their backbones of electron-rich and electron-deficient fragments contributes to the presence of low-lying excited states that are expected to display significant charge-transfer character. While conventional hybrid functionals are known to provide unsatisfactory results for charge-transfer excitations at the time-dependent DFT level, long-range corrected (LRC) functionals have been reported to give improved descriptions in a number of systems. Here, we use such LRC functionals, considering both tuned and default range-separation parameters, to characterize the absorption spectra of low-optical-gap systems of interest. Our results indicate that tuned LRC functionals lead to simulated optical-absorption properties in good agreement with experimental data. Importantly, the lowest-lying excited states (excitons) are shown to present a much more localized nature than initially anticipated. © 2012 the Owner Societies.

  9. THE END OF HELIUM REIONIZATION AT z ≅ 2.7 INFERRED FROM COSMIC VARIANCE IN HST/COS He II Lyα ABSORPTION SPECTRA

    International Nuclear Information System (INIS)

    Worseck, Gabor; Xavier Prochaska, J.; McQuinn, Matthew; Dall'Aglio, Aldo; Wisotzki, Lutz; Fechner, Cora; Richter, Philipp; Hennawi, Joseph F.; Reimers, Dieter

    2011-01-01

    We report on the detection of strongly varying intergalactic He II absorption in HST/COS spectra of two z em ≅ 3 quasars. From our homogeneous analysis of the He II absorption in these and three archival sightlines, we find a marked increase in the mean He II effective optical depth from eff,He i i >≅1 at z ≅ 2.3 to eff,He i i >∼>5 at z ≅ 3.2, but with a large scatter of 2∼ eff,He i i ∼ 2.7, probably indicating He II reionization was incomplete at z reion ∼> 2.7. Likewise, recent three-dimensional numerical simulations of He II reionization qualitatively agree with the observed trend only if He II reionization completes at z reion ≅ 2.7 or even below, as suggested by a large τ eff,He i i ∼>3 in two of our five sightlines at z < 2.8. By doubling the sample size at 2.7 ∼< z ∼< 3, our newly discovered He II sightlines for the first time probe the diversity of the second epoch of reionization when helium became fully ionized.

  10. X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

    Science.gov (United States)

    McKeown, David A.; Gan, Hao; Pegg, Ian L.

    2017-05-01

    Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.

  11. Induced absorption spectra of the infrared fundamental band of molecular deuterium at 77 K: S1( J)+S0( J) transitions

    International Nuclear Information System (INIS)

    Gillard, P.G.; Prasad, R.D.G.; Reddy, S.P.

    1984-01-01

    The collision-induced spectra of the fundamental band of normal D 2 in the high frequency region 3200--3700 cm -1 were recorded for gas densities in the range 80--140 amagat at 77 K with a 2 m absorption cell. The contribution to the intensity of the band in this region comes from the high frequency wings of quadrupolar transitions S 1 ( J) and Q 1 ( J)+S 0 ( J) with J = 0 and 1, and from the group of transitions S 1 (2) and Q 1 ( J)+S 0 (2) with J = 0, 1, and 2 as well as from the relatively weaker double rotational transitions of the type S 1 ( J)+S 0 ( J); the latter transitions arise from the intermolecular interaction between the anisotropic component of the polarizability of one of the colliding pairs of molecules and the quadrupole field of the other. The experimental profiles were analyzed by assuming appropriate line shape functions and using the theoretical matrix elements of the quadrupole moment, isotropic polarizability, and anisotropy of polarizability of the D 2 molecule. From this analysis the characteristic half-width parameters delta/sub q/2 and delta/sub q/4 of the quadrupolar transitions and the binary and ternary absorption coefficients of the S 1 ( J)+S 0 ( J) transitions have been obtained. The experimental value of the binary absorption coefficient of S 1 (0)+S 0 (0) is (2.2 +- 0.1) x 10 -9 cm -1 amagat -2 and the corresponding theoretical value is 1.53 x 10 -9 cm -1 amagat -2

  12. NMR and XAS Study of Fe-Mo Double Perovskites

    International Nuclear Information System (INIS)

    Zajac, D.A.; Kapusta, C.; Borowiec, M.; Sikora, M.; Marquina, C.; Blasco, J.; Ibarra, M.R.

    2005-01-01

    to a dependence of the Mo magnetic moment on the averaged ionic radius of the alkaline earth. The highest Mo moment is observed for Sr 2 FeMoO 6 (0.60(3) μ B ), where the Sr ionic radius corresponds to f of 1.007. The Mo magnetic moment derived from the value of the Mo hyperfine field decreases with the tolerance factor going away from f=1 and amounts to 0.48(3) μ B for SrBaFeMoO 6 (f=1.039), 0.58(3) μ B for Ba 2 FeMoO 6 (f=1.07) and 0.58(3) μ B for Ca 2 FeMoO 6 (f=0.974). A similar dependence on f is also observed for TC. This indicates that the strength of magnetic interaction is related to the magnetic moment (and the corresponding 4d electron density) at the molybdenum site. A higher TC is observed for a larger value of the magnetic moment (larger electron density) at Mo. Temperature dependence of the Mo hyperfine field exhibits a predominant T5/2 character, which indicates a half metallic nature of the compounds. X-ray absorption measurements in the XANES range have been carried out at 300 K in the transmission mode at the A1 station in Hasylab/DESY Hamburg. The edge energies correspond to an intermediate valence state of Fe, between 2.5+ and 3+ for all the investigated DP compounds, with a dependence on f. For the compounds Ba 2 FeMoO 6 and SrBaFeMoO 6 a two step feature of the absorption edge is observed. The step at higher energies is attributed to the iron valence states close to Fe 3+ , whereas the lower energy one is attributed to an intermediate Fe valence, in analogy with the XAS spectrum of Fe 3 O 4 . XANES measurements have also been carried out at the Mo K edge and the results show an intermediate valence state of Mo, between 5 + and 6 + . A change of the edge energy with f is observed, with an opposite tendency to that obtained for Fe. This indicates the occurrence of an electron density redistribution between the Fe and Mo sites dependent on the structural factor. The results of NMR measurements are compared to those of XANES study and a

  13. DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

    Science.gov (United States)

    2017-10-31

    VC-nH2O for Small and Water-Dominated Molecular Clusters October 31, 2017 Approved for public release; distribution is unlimited. L. Huang S.g...Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters L. Huang,1 S.G...nH2O molecular clusters using density function theory (DFT). DFT can provide interpretation of absorption spectra with respect to molecular

  14. First X-Ray absorption spectroscopy results on Aeolian dust archived in Antarctica and Alpine firn cores

    Science.gov (United States)

    Marcelli, A.; Maggi, V.; Cibin, G.; Sala, M.; Marino, F.; Delmonte, B.

    2006-12-01

    We present the first x-ray absorption spectroscopy (XAS) data at the Fe K-edge collected on insoluble mineral dust from Talos Dome firn core (TDC, 159°04'E, 72°46'S, 2316 m a.s.l., mean accumulation rate 8 g cm-2 yr- 1), drilled in the framework of the International Trans Antarctic Scientific Expedition (ITASE), and from a Colle del Lys 2003 firn core (CDL03, 45°92'N, 7°86'E, 4248m a.s.l., mean accumulation rate 134 g cm-2 yr-1, Lys Glacier, Mt. Rosa, Italy). The low concentration of mineral particles, obtained by filtering each firn core melted samples on Nuclepore membranes in a 1000 class clean room, required a specific procedure to prepare the samples necessary to the successful collection of the XAS data. The firn samples were decontaminated in clean room under laminar flow bench by means of a ceramic knife and discarding the external part of the cores. Analyses of the insoluble particle content were performed by particle counter Beckman CounterãMultisizer III in order to defined concentration and size distribution of particles in each samples. A dedicated HV experimental chamber, devoted to the realization of XAS experiments on very low absorber concentration samples, was developed and realized in the framework of the CryoAlp collaboration at IMONT, the Italian National Institute for Mountains. The original experimental setup, thanks to the presence of an in-vacuum sample micromanipulator and special sample alignment and docking system installed for these experiments at the Stanford Synchrotron Radiation Laboratory at the beamline 6-2, allows both normal-incidence X-ray Fluorescence detection using a Ketek SDD detector having an energy resolution of about 150 eV and extremely low energy detection limit, and Total X-ray Reflection Fluorescence and Absorption Spectroscopy measurements. The high quality of the XANES experiments performed, using both normal incidence and Total Reflection XAS measurements, allowed recognizing iron-inclusion mineral fractions

  15. Utilization of synchrotron radiation in analytical chemistry. Soft X-ray emission and absorption spectroscopy

    International Nuclear Information System (INIS)

    Muramatsu, Yasuji

    2015-01-01

    Synchrotron soft X-ray spectroscopy includes three major types of spectroscopy such as X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), and X-ray photoelectron spectroscopy (XPS). This paper takes up XAS and XES of soft X-rays, and briefly describes the principle. XAS is roughly classified into XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure), and XANES is mainly used in the analysis based on XAS of soft X-rays. As the examples of the latest soft X-ray analyses, the following are introduced: (1) bandgap of boron implantation diamond and the local structure of boron, (2) catalytic sites in solid fuel cell carbon electrode, and (3) soft X-ray analysis under atmospheric pressure. (A.O.)

  16. Compressed shell conditions extracted from spectroscopic analysis of Ti K-shell absorption spectra with evaluation of line self-emission

    Energy Technology Data Exchange (ETDEWEB)

    Johns, H. M.; Mancini, R. C.; Hakel, P.; Nagayama, T. [Physics Department, University of Nevada, Reno, 1664 N. Virginia St., Reno, Nevada 89557 (United States); Smalyuk, V. A.; Regan, S. P.; Delettrez, J. [Laboratory for Laser Energetics, University of Rochester, 250 E. River Road, Rochester, New York 14623 (United States)

    2014-08-15

    Ti-doped tracer layers embedded in the shell at varying distances from the fuel-shell interface serve as a spectroscopic diagnostic for direct-drive experiments conducted at OMEGA. Detailed modeling of Ti K-shell absorption spectra produced in the tracer layer considers n = 1–2 transitions in F- through Li-like Ti ions in the 4400–4800 eV range, both including and excluding line self-emission. Testing the model on synthetic spectra generated from 1-D LILAC hydrodynamic simulations reveals that the model including self-emission best reproduces the simulation, while the model excluding self-emission overestimates electron temperature T{sub e} and density N{sub e} to a higher degree for layers closer to the core. The prediction of the simulation that the magnitude of T{sub e} and duration of Ti absorption will be strongly tied to the distance of the layer from the core is consistent with the idea that regions of the shell close to the core are more significantly heated by thermal transport out of the hot dense core, but more distant regions are less affected by it. The simulation predicts more time variation in the observed T{sub e}, N{sub e} conditions in the compressed shell than is observed in the experiment, analysis of which reveals conditions remain in the range T{sub e} = 400–600 eV and N{sub e} = 3.0–10.0 × 10{sup 24} cm{sup −3} for all but the most distant Ti-doped layer, with error bars ∼5% T{sub e} value and ∼10% N{sub e} on average. The T{sub e}, N{sub e} conditions of the simulation lead to a greater degree of ionization for zones close to the core than occurs experimentally, and less ionization for zones far from the core.

  17. Theoretical modeling of deuteration-induced shifts of the 0-0 bands in absorption spectra of selected aromatic amines: the role of the double-well potential.

    Science.gov (United States)

    Andrzejak, Marcin; Kolek, Przemysław

    2013-12-05

    The harmonic approximation fails for inversion of the NH2 group in the ground state of aromatic amines as this vibration is characterized by a symmetric double-well potential with relatively small energy barrier. In such cases, the standard harmonic vibrational analysis is inapplicable: the inversion frequency calculated for the bottom of the potential well is strongly overestimated, while it attains imaginary values for the planar conformation of the molecule. The model calculations are discussed taking explicitly into account the presence of the double-well potential. The study is initially focused on reproduction of the deuteration-induced shifts of the 0-0 absorption band for anthranilic acid. The (incorrect) harmonic frequency of the NH2 inversion is replaced by a better one, obtained from numerical calculations employing a simple, quartic-quadratic model for the double-well potential, which is parametrized using just the harmonic frequency of the inversion and the height of the energy barrier. This operation brings theoretical results to qualitative agreement with experiment. A still better match is achieved with a modified version of the model that accounts for mixing of the NH2 inversion mode with other normal modes while retaining the initial simplicity of one-dimensional approach. The corrected results show surprisingly good accuracy, with deviations of the calculated shifts from the experimental values reduced to less than 5 cm(-1). In order to test the performance of the model for systems with higher energy barrier for the NH2 inversion, we have measured the LIF excitation spectra of three different amminobenzonitriles. Partial assignment of the 0-0 bands has been achieved based on their relative intensities for samples with different isotopic exchange ratios. Calculated shifts are in excellent agreement with experimental values for the identified bands. Theoretical predictions are used to complete the assignment of the 0-0 bands in the spectra of the

  18. Four-Component Damped Density Functional Response Theory Study of UV/Vis Absorption Spectra and Phosphorescence Parameters of Group 12 Metal-Substituted Porphyrins.

    Science.gov (United States)

    Fransson, Thomas; Saue, Trond; Norman, Patrick

    2016-05-10

    The influences of group 12 (Zn, Cd, Hg) metal-substitution on the valence spectra and phosphorescence parameters of porphyrins (P) have been investigated in a relativistic setting. In order to obtain valence spectra, this study reports the first application of the damped linear response function, or complex polarization propagator, in the four-component density functional theory framework [as formulated in Villaume et al. J. Chem. Phys. 2010 , 133 , 064105 ]. It is shown that the steep increase in the density of states as due to the inclusion of spin-orbit coupling yields only minor changes in overall computational costs involved with the solution of the set of linear response equations. Comparing single-frequency to multifrequency spectral calculations, it is noted that the number of iterations in the iterative linear equation solver per frequency grid-point decreases monotonously from 30 to 0.74 as the number of frequency points goes from one to 19. The main heavy-atom effect on the UV/vis-absorption spectra is indirect and attributed to the change of point group symmetry due to metal-substitution, and it is noted that substitutions using heavier atoms yield small red-shifts of the intense Soret-band. Concerning phosphorescence parameters, the adoption of a four-component relativistic setting enables the calculation of such properties at a linear order of response theory, and any higher-order response functions do not need to be considered-a real, conventional, form of linear response theory has been used for the calculation of these parameters. For the substituted porphyrins, electronic coupling between the lowest triplet states is strong and results in theoretical estimates of lifetimes that are sensitive to the wave function and electron density parametrization. With this in mind, we report our best estimates of the phosphorescence lifetimes to be 460, 13.8, 11.2, and 0.00155 s for H2P, ZnP, CdP, and HgP, respectively, with the corresponding transition

  19. Behavior of fission gases in nuclear fuel: XAS characterization of Kr in UO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Martin, P.M., E-mail: Philippe-m.martin@cea.fr [CEA, DEN, Cadarache DEC/SESC, F-13108 St-Paul-Lez-Durance Cedex (France); Vathonne, E.; Carlot, G.; Delorme, R.; Sabathier, C.; Freyss, M.; Garcia, P.; Bertolus, M. [CEA, DEN, Cadarache DEC/SESC, F-13108 St-Paul-Lez-Durance Cedex (France); Glatzel, P. [European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, 38043 Grenoble (France); Proux, O. [OSUG, Observatoire des Sciences de l’Univers de Grenoble, CNRS and Université Joseph Fourier, BP 53, 38041 Grenoble Cedex 9 (France)

    2015-11-15

    X-ray Absorption Spectroscopy (XAS) was used to study the behavior of krypton as a function of its concentration in UO{sub 2} samples implanted with Kr ions. For a 0.5 at.% krypton local concentration, by combining XAS results and DFT + U calculations, we show that without any thermal treatment Kr atoms are mainly incorporated in the UO{sub 2} lattice as single atoms inside a neutral bound Schottky defect with O vacancies aligned along the (100) direction (BSD1). A thermal treatment at 1273 K induces the precipitation of dense Kr nano-aggregates, most probably solid at room temperature. In addition, 26 ± 2% of the Kr atoms remain inside BSD1 showing that Kr-BSD1 complex is stable up to this temperature. Consequently, the (in-)solubility of krypton in UO{sub 2} has to be re-evaluated. For high Kr concentration (8 at.%), XAS signals show that Kr atoms have precipitated in nanometer-sized aggregates with internal densities ranging between 4.15(7) g cm{sup −3} and 3.98(5) g cm{sup −3} even after annealing at 873 K. By neglecting the effect due to the UO{sub 2} matrix, the corresponding krypton pressures at 300 K were equal to 2.6(3) GPa and 2.0(2) GPa, respectively. After annealing at 1673 K, regardless of the initial Kr concentration, a bi-modal distribution is observed with solid nano-aggregates even at room temperature and larger cavities only partially filled with Kr. These results are very close to those observed in UO{sub 2} fuel irradiated in reactor. In this study we show that a rare gas can be used as a probe to investigate the defect creation and their stability in UO{sub 2}.

  20. Atomistic absorption spectra and non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model

    Science.gov (United States)

    Glowacki, David

    Recently, we outlined an efficient multi-tiered parallel excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground/excited state energies and gradients of large supramolecular complexes in atomistic detail. In this paper, we apply our ab initioexciton framework to the 27 coupled bacteriocholorophyll-a chromophores which make up the LH2 complex, using it to compute linear absorption spectra and short-time, on-the-fly nonadiabatic surface-hopping (SH) dynamics of electronically excited LH2. Our ab initio exciton model includes two key parameters whose values are determined by fitting to experiment: d, which is added to the diagonal elements, corrects for the error in TDDFT vertical excitation energies on a single chromophore; and e, which occurs on the off-diagonal matrix elements, describes the average dielectric screening of the inter-chromophore transition-dipole coupling. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, best-fit values of both d and e were obtained by fitting to the thermally broadened experimental absorption spectrum within the Frank-Condon approximation, providing a linear absorption spectrum that agrees reasonably well with the experimental observations. We follow the nonadiabatic dynamics using surface hopping to construct time-resolved visualizations of the EET dynamics in the sub-picosecond regime following photoexcitation. This provides some qualitative insight into the excitonic energy transfer (EET) that results from atomically resolved vibrational fluctuations of the chromophores. The dynamical picture that emerges is one of rapidly fluctuating eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the underlying chromophore vibrational dynamics. The eigenstate fluctuations arise from disorder in both the diagonal chromophore site energies and the off-diagonal inter

  1. X-ray absorption spectroscopy of semiconductors

    CERN Document Server

    Ridgway, Mark

    2015-01-01

    X-ray Absorption Spectroscopy (XAS) is a powerful technique with which to probe the properties of matter, equally applicable to the solid, liquid and gas phases. Semiconductors are arguably our most technologically-relevant group of materials given they form the basis of the electronic and photonic devices that now so widely permeate almost every aspect of our society. The most effective utilisation of these materials today and tomorrow necessitates a detailed knowledge of their structural and vibrational properties. Through a series of comprehensive reviews, this book demonstrates the versatility of XAS for semiconductor materials analysis and presents important research activities in this ever growing field. A short introduction of the technique, aimed primarily at XAS newcomers, is followed by twenty independent chapters dedicated to distinct groups of materials. Topics span dopants in crystalline semiconductors and disorder in amorphous semiconductors to alloys and nanometric material as well as in-sit...

  2. Infrared Absorption Spectra, Radiative Efficiencies, and Global Warming Potentials of Newly-Detected Halogenated Compounds: CFC-113a, CFC-112 and HCFC-133a

    Directory of Open Access Journals (Sweden)

    Maryam Etminan

    2014-07-01

    Full Text Available CFC-113a (CF3CCl3, CFC-112 (CFCl2CFCl2 and HCFC-133a (CF3CH2Cl are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP. The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012 concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100, are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a.

  3. Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor

    International Nuclear Information System (INIS)

    Zhu, Jin; Li, Wenbin; Zhu, Mao; Zhang, Wei; Niu, Wencheng; Liu, Guohua

    2014-01-01

    The localized surface plasmon resonances (LSPRs) of gold particles assembled on a crystal plate are a powerful tool for biological sensors. Here, we prepare gold colloids in different pH solutions. We monitor the effects of the particle radius and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of about 3°) crystal plates supporting gold nanoparticles. The surface morphologies were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis) spectroscopy, and atomic force microscopy (AFM). The results showed that the gold particle coverage decreases with increasing pH value of the gold colloid solution. This phenomenon demonstrates that self-assembled gold surfaces were formed via the electrostatic adsorption of gold particles on the positively charged, ionized amino groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles with different coverage degree on the crystal plates showed that the LSPR properties are highly dependent on pH

  4. Growth of block copolymer stabilized metal nanoparticles probed simultaneously by in situ XAS and UV-Vis spectroscopy.

    Science.gov (United States)

    Nayak, C; Bhattacharyya, D; Jha, S N; Sahoo, N K

    2016-01-01

    The growth of Au and Pt nanoparticles from their respective chloride precursors using block copolymer-based reducers has been studied by simultaneous in situ measurement of XAS and UV-Vis spectroscopy at the energy-dispersive EXAFS beamline (BL-08) at INDUS-2 SRS at RRCAT, Indore, India. While the XANES spectra of the precursor give real-time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed at the intermediate stages of growth. The growth kinetics of both types of nanoparticles are found to be almost similar and are found to follow three stages, though the first stage of nucleation takes place earlier in the case of Au than in the case of Pt nanoparticles due to the difference in the reduction potential of the respective precursors. The first two stages of the growth of Au and Pt nanoparticles as obtained by in situ XAS measurements could be corroborated by simultaneous in situ measurement of UV-Vis spectroscopy also.

  5. DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells

    Science.gov (United States)

    Rezvani, M.; Darvish Ganji, M.; Jameh-Bozorghi, S.; Niazi, A.

    2018-04-01

    In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω+) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C60-Porphyrine-Metalloporphyrine (C60-P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C60-P-Mptriad system due to C60-Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In

  6. XAS study of TiO2-based nanomaterials

    Science.gov (United States)

    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.

  7. Speciation of Selenium in Stream Insects Using X-Ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Andrahennadi, R.; Wayland, M.; Pickering, I.J.

    2009-05-28

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  8. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering [University of Saskatchewan, Saskatoon, SK (Canada). Department of Geological Sciences

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  9. Study on the interactions of antiemetic drugs and 12-tungstophosphoric acid by absorption and resonance Rayleigh scattering spectra and their analytical applications

    Science.gov (United States)

    Wang, Yaqiong; Liu, Shaopu; Liu, Zhongfang; Yang, Jidong; Hu, Xiaoli

    2013-03-01

    In 0.1 mol L-1 HCl medium, antiemetic drugs (ATM), such as granisetron hydrochloride (GS) and tropisetron hydrochloride (TS), reacted with H3PW12O40·nH2O and formed 3:1 ion-association complex of [(ATM)3PW12O40], then self-aggregated into nanoparticles-[(ATM)3PW12O40]n with an average size of 100 nm. The reaction resulted in the enhancement of resonance Rayleigh scattering (RRS) and the absorption spectra. The increments of scattering intensity (ΔIRRS) and the change of absorbance (ΔA) were both directly proportional to the concentrations of ATM in certain ranges. Accordingly, two new RRS and spectrophotometric methods were proposed for ATM detection. The detection limits (3σ) of GS and TS were 3.2 ng mL-1 and 4.0 ng mL-1(RRS method), 112.5 ng mL-1 and 100.0 ng mL-1(spectrophotometric method). These two methods were applied to determine GS in orally disintegrating tablets and the results were in good agreement with the official method. The ground-state geometries and electronic structures of GS and TS were optimized by the hybrid density functional theory (DFT) method and the shape of [(ATM)3PW12O40]n was characterized by atomic force microscopy (AFM). Take the RRS method with higher sensitivity as an example, the reaction mechanism and the reasons for enhancement of scattering were discussed.

  10. Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

    Science.gov (United States)

    Adrowski, Michael J.; Mason, W. Roy

    1997-03-26

    Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

  11. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

  12. Local hydrated structure of an Fe2+/Fe3+ aqueous solution: an investigation using a combination of molecular dynamics and X-ray absorption fine structure methods

    International Nuclear Information System (INIS)

    Ye Qing; Zhou Jing; Zhao Haifeng; Chen Xing; Chu Wangsheng; Zheng Xusheng; Marcelli, Augusto; Wu Ziyu

    2013-01-01

    The hydrated shell of both Fe 2+ and Fe 3+ aqueous solutions are investigated by using the molecular dynamics (MD) and X-ray absorption structure (XAS) methods. The MD simulations show that the first hydrated shells of both Fe 2+ and Fe 3+ are characterized by a regular octahedron with an Fe-O distance of 2.08Å for Fe 2+ and 1.96Å for Fe 3+ , and rule out the occurrence of a Jahn-Teller distortion in the hydrated shell of an Fe 2+ aqueous solution. The corresponding X-ray absorption near edge fine structure (XANES) calculation successfully reproduces all features in the XANES spectra in Fe 2+ and Fe 3+ aqueous solution. A feature that is located at energy 1 eV higher than the white line (WL) in an Fe 3+ aqueous solution may be assigned to the contribution of the charge transfer. (authors)

  13. 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

    Science.gov (United States)

    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.

  14. Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

    Science.gov (United States)

    Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

    2018-05-01

    During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

  15. Development of Ta-based Superconducting Tunnel Junction X-ray Detectors for Fluorescence XAS

    International Nuclear Information System (INIS)

    Friedrich, S.; Drury, O.; Hall, J.; Cantor, R.

    2009-01-01

    We are developing superconducting tunnel junction (STJ) soft X-ray detectors for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS). Our 36-pixel Nb-based STJ spectrometer covers a solid angle (Omega)/4π ∼ 10 -3 , offers an energy resolution of ∼10-20 eV FWHM for energies up to ∼1 keV, and can be operated at total count rates of ∼10 6 counts/s. For increased quantum efficiency and cleaner response function, we have now started the development of Ta-based STJ detector arrays. Initial devices modeled after our Nb-based STJs have an energy resolution below 10 eV FWHM for X-ray energies below 1 keV, and pulse rise time discrimination can be used to improve their response function for energies up to several keV. We discuss the performance of the Ta-STJs and outline steps towards the next-generation of large STJ detector arrays with higher sensitivity.

  16. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J., E-mail: saykally@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Shih, Orion [National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China); Rizzuto, Anthony M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Prendergast, David [The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-08-28

    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 spectroscopy (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.

  17. Spectra of alkali atoms

    International Nuclear Information System (INIS)

    Santoso, Budi; Arumbinang, Haryono.

    1981-01-01

    Emission spectra of alkali atoms has been determined by using spectrometer at the ultraviolet to infra red waves range. The spectra emission can be obtained by absorption spectrophotometric analysis. Comparative evaluations between experimental data and data handbook obtained by spark method were also presented. (author tr.)

  18. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    International Nuclear Information System (INIS)

    Szilagyi, Robert K.; Schwab, David E.

    2005-01-01

    X-ray absorption spectroscopy at the sulfur K-edge (2.4-2.6 keV) provides a sensitive and specific technique to identify S-nitroso compounds, which have significance in nitric oxide-based cell signaling. Unique spectral features clearly distinguish the S-nitroso-form of a cysteine residue from the sulfhydryl-form or from a methionine thioether. Comparison of the sulfur K-edge spectra of thiolate, thiol, thioether, and S-nitroso thiolate compounds indicates high sensitivity of energy positions and intensities of XAS pre-edge features as determined by the electronic environment of the sulfur absorber. A new experimental setup is being developed for reaching the in vivo concentration range of S-nitroso thiol levels in biological samples

  19. A combined in situ XAS-XRPD-Raman study of Fischer-Tropsch synthesis over a carbon supported Co catalyst

    DEFF Research Database (Denmark)

    Tsakoumis, Nikolaos E.; Dehghan, Roya; Johnsen, Rune

    2013-01-01

    A cobalt based Fischer-Tropsch synthesis (FTS) catalyst, supported on a carbon nanofibers/carbon felt composite (Co/CNF/CF) was studied in situ at realistic conditions. The catalyst was monitored by Xray absorption spectroscopy (XAS), high-resolution X-ray powder diffraction (HR-XRPD) and Raman...... spectroscopy, while changes in the gas phase were observed by mass spectrometry (MS). Transmission electron microscopy (TEM) was also applied to characterise the catalyst. The catalyst has a bimodal particle size distribution and exhibits a high deactivation rate. During the in situ study the catalyst appears...... to reduce further at the induction period of FTS, while crystallite growth is been detected in the same period. At steady state FTS the amount of metallic Co is constant. A change in the volumetric flow towards higher conversions did not affect the degree of reduction or the crystallite size of the catalyst...

  20. XAS study of the local environment of impurities in doped TiO{sub 2} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez Torres, C.E. [Departamento de Fisica e IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina)]. E-mail: torres@fisica.unlp.edu.ar; Cabrera, A.F. [Departamento de Fisica e IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Errico, L.A. [Departamento de Fisica e IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Duhalde, S. [Lab. de Ablacion Laser, FI-UBA (Argentina); Renteria, M. [Departamento de Fisica e IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Golmar, F. [Lab. de Ablacion Laser, FI-UBA (Argentina); Sanchez, F.H. [Departamento de Fisica e IFLP (CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina)

    2007-09-01

    In this work, we present an X-ray absorption spectroscopy (XAS) characterization of the local environment of the impurity in room temperature ferromagnetic (RTF) anatase TiO{sub 2} thin films doped with Co, Ni, Cu, or Zn, deposited on LaAlO{sub 3} substrate by pulsed laser deposition (PLD). It was found that there is a considerable amount of impurity atoms substituting Ti in TiO{sub 2} anatase, although the presence of metal transition monoxide clusters can not be discarded. From our results, we infer that the observed RT ferromagnetism of the samples could be assigned to the metal transition atoms replacing Ti in TiO{sub 2} anatase.

  1. Franck-Condon Simulations including Anharmonicity of the Ã(1)A''-X̃(1)A' Absorption and Single Vibronic Level Emission Spectra of HSiCl and DSiCl.

    Science.gov (United States)

    Mok, Daniel W K; Lee, Edmond P F; Chau, Foo-Tim; Dyke, John M

    2009-03-10

    RCCSD(T) and/or CASSCF/MRCI calculations have been carried out on the X̃(1)A' and Ã(1)A'' states of HSiCl employing basis sets of up to the aug-cc-pV5Z quality. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HSiCl. Franck-Condon factors which include allowance for anharmonicity and Duschinsky rotation between these two states of HSiCl and DSiCl were calculated employing RCCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate the Ã(1)A'' ← X̃(1)A' absorption and Ã(1)A'' → X̃(1)A' single vibronic level (SVL) emission spectra of HSiCl and DSiCl. Simulated absorption and experimental LIF spectra, and simulated and observed Ã(1)A''(0,0,0) → X̃(1)A' SVL emission spectra, of HSiCl and DSiCl are in very good agreement. However, agreement between simulated and observed Ã(1)A''(0,1,0) → X̃(1)A' and Ã(1)A''(0,2,1) → X̃(1)A' SVL emission spectra of DSiCl is not as good. Preliminary calculations on low-lying excited states of HSiCl suggest that vibronic interaction between low-lying vibrational levels of the Ã(1)A'' state and highly excited vibrational levels of the ã(3)A'' is possible. Such vibronic interaction may change the character of the low-lying vibrational levels of the Ã(1)A'' state, which would lead to perturbation in the SVL emission spectra from these vibrational levels.

  2. Absorption infrared spectra of interaction products of cyclic polyethers 18-crown-6 and dibenzo-18-crown-6 with uranyl dinitrate hexahydrate

    International Nuclear Information System (INIS)

    Chumaevskij, N.A.; Belomestnykh, V.I.; Razgonyaeva, G.A.; Shabel'nik, K.S.; Afanas'eva, E.E.

    1988-01-01

    Using the method of IR spectroscopy it is established that during interaction of uranyl nitrate hexahydrate (UNH) with crown-ethers under investigation macrocycles adhere to UO 2 2+ via hydrogen bonds between water molecules and oxygen of polyethers. Interaction of UNH with the above-mentioned crowns leads to conformational rearrangement of cycles of polyethers and improvement of their symmetry, reflecting in noticeable simplification of IR spectra of interaction products as compared to spectra of initial cyclic polyethers

  3. Tin Valence and Local Environments in Silicate Glasses as Determined From X-ray Absorption Spectroscopy

    International Nuclear Information System (INIS)

    McKeown, D.; Buechele, A.; Gan, H.; Pegg, I.

    2008-01-01

    X-ray absorption spectroscopy (XAS) was used to characterize the tin (Sn) environments in four borosilicate glass nuclear waste formulations, two silicate float glasses, and three potassium aluminosilicate glasses. Sn K-edge XAS data of most glasses investigated indicate Sn4+O6 units with average Sn-O distances near 2.03 Angstroms. XAS data for a float glass fabricated under reducing conditions show a mixture of Sn4+O6 and Sn2+O4 sites. XAS data for three glasses indicate Sn-Sn distances ranging from 3.43 to 3.53 Angstroms, that suggest Sn4+O6 units linking with each other, while the 4.96 Angstroms Sn-Sn distance for one waste glass suggests clustering of unlinked Sn4+O6 units.

  4. Effects of tattoo ink's absorption spectra and particle size on cosmetic tattoo treatment efficacy using Q-switched Nd:YAG laser.

    Science.gov (United States)

    Leu, Fur-Jiang; Huang, Chuen-Lin; Sue, Yuh-Mou; Lee, Shao-Chen; Wang, Chia-Chen

    2015-01-01

    The mechanisms responsible for variable responses of cosmetic tattoos to Q-switched laser removal treatment remain unclear. We sought to investigate the properties of tattoo inks that may affect the efficacy of laser-assisted tattoo removal. The absorption of white, brown, and black inks before and after Q-switched neodymium-doped yttrium aluminum garnet laser irradiation were analyzed by a reflectance measurement system. Rats were tattooed using the three inks and treated with the same laser for two sessions. Skin biopsies were taken from the treated and untreated sites. Black ink showed strong absorption, reduced after laser irradiation, over the entire spectrum. White ink had low absorption over the visible light spectrum, and brown ink had strong absorption at 400-550 nm wavelengths. White and brown inks turned dark after laser exposure, and the absorption of laser-darkened inks were intermediate between their original color and black ink. White, brown, and black tattoos in rat skin achieved poor, fair to good, and excellent responses to laser treatment, respectively. Transmission electron microscopy showed that white tattoo particles were the largest, brown were intermediate, and black were the smallest before laser. After laser treatment, white and brown tattoo particles were mixtures of large and small particles, while black particles showed overall reduction in number and size. Black tattoo ink's excellent response to Q-switched lasers was associated with its strong absorption and small particle size. White tattoo ink's poor response was associated with its poor absorption, even after laser darkening, and large particle size.

  5. Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

    Science.gov (United States)

    Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

    2009-04-01

    Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of

  6. Solvatochromic effect studies on the absorption spectra of 4-((2-ethylphenyl)diazenyl)benzene-1,3-diol and 2-((2-ethylphenyl)diazenyl)benzene-1,3,5-triol molecules

    Energy Technology Data Exchange (ETDEWEB)

    Guelseven, Yadigar; Tasal, Erol; Sidir, Isa [Department of Physics, Faculty of Arts and Sciences, Eskisehir Osmangazi University, Eskisehir 26480 (Turkey); Guengoer, Tayyar [Department of Physics, Faculty of Arts and Sciences, Akdeniz University, Antalya (Turkey); Berber, Halil [Department of Chemistry, Faculty of Sciences, Anadolu University, Eskisehir (Turkey); Oegretir, Cemil [Department of Chemistry, Faculty of Arts and Sciences, Eskisehir Osmangazi University, Eskisehir (Turkey)

    2009-06-15

    The electronic absorption spectra of 4-((2-ethylphenyl)diazenyl)benzene-1,3-diol and 2-((2-ethylphenyl)diazenyl)benzene-1,3,5-triol molecules in the nine different solvent variable electronic characters have been recorded. The solvent dependent maximum absorption band ({pi}-{pi}* transitions) shifts, {nu}{sub max}, were analyzed using a wide range of parameters such as refractive index, dielectric constant and Kamlet-Taft parameters [hydrogen bond donating ability ({alpha}) and hydrogen bond accepting ability ({beta})]. The electronic transitions are assigned and the solvent-induced spectral shifts have been analyzed in relation to the different solute-solvent interaction mechanism using computational chemistry. The intermolecular interaction types in the azobenzene derivatives solutions have been established on the basis of a multiple linear regression analysis. The fitting coefficients obtained from this analysis allowed us to estimate the contribution of each type of interactions to the total spectral shifts in the studied solutions. (author)

  7. Development of program package for investigation and modeling of carbon nanostructures in diamond like carbon films with the help of Raman scattering and infrared absorption spectra line resolving

    Science.gov (United States)

    Hayrapetyan, David B.; Hovhannisyan, Levon; Mantashyan, Paytsar A.

    2013-04-01

    The analysis of complex spectra is an actual problem for modern science. The work is devoted to the creation of a software package, which analyzes spectrum in the different formats, possesses by dynamic knowledge database and self-study mechanism, performs automated analysis of the spectra compound based on knowledge database by application of certain algorithms. In the software package as searching systems, hyper-spherical random search algorithms, gradient algorithms and genetic searching algorithms were used. The analysis of Raman and IR spectrum of diamond-like carbon (DLC) samples were performed by elaborated program. After processing the data, the program immediately displays all the calculated parameters of DLC.

  8. Yb:Lu{sub 2}O{sub 3} hydrothermally-grown single-crystal and ceramic absorption spectra obtained between 298 and 80 K

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Cheryl A. [Snake Creek Lasers LLC, 26741 State Route 267, Friendsville, PA 18818 (United States); Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University, Clemson, SC 29634-0973 (United States); Brown, David C., E-mail: dbrown@snakecreeklasers.com [Snake Creek Lasers LLC, 26741 State Route 267, Friendsville, PA 18818 (United States); Sanjeewa, Liurukara D.; McMillen, Colin D.; Kolis, Joseph W. [Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University, Clemson, SC 29634-0973 (United States)

    2016-06-15

    The hydrothermal growth, doping, and low temperature spectral characterization of Yb doped Lu{sub 2}O{sub 3} was investigated. The absorption of the lutetia-based sesquioxide laser material Yb:Lu{sub 2}O{sub 3} at temperatures of 80, 150, 200, 250, and 298 K, in the wavelength range of 850–1100 nm are reported. Data for both single crystal and ceramic Yb:Lu{sub 2}O{sub 3} were obtained. The resulting absorption cross-section data will enable the further evaluation of Yb:Lu{sub 2}O{sub 3} as a very promising high power cryogenic laser material.

  9. An investigation on the effect of gamma-irradiation on the optical absorption spectra in Cu(II) doped ammonium Tetrachlorozincate (ATZC) single crystals

    International Nuclear Information System (INIS)

    Abu El-Fadl, A.; Mohamad, G.A.; Abd El-Sttar, M.

    2003-01-01

    Optical transmittance measurements were carried out on Ammonium tetrachlorozincate (ATZC) crystals doped with small concentrations of Cu 2+ ions and irradiated with different doses of gamma-radiation. The absorption coefficient (alpha) and the extinction coefficient (K) of unirradiated and irradiated ATZC crystals were calculated. Valued of the allowed indirect optical energy gap (E g ) of ATZC were calculated as a function of gamma-dose. The effect of gamma irradiation is to increase in the absorption coefficient value and to decrease in E g value. The results could be explained in the fact that gamma irradiation produces defects of ionizing type because of internal irradiation with photon or Compton electrons

  10. Theoretical interpretation for 2p − nd absorption spectra of iron, nickel, and copper in X-ray range measured at the LULI2000 facility

    Directory of Open Access Journals (Sweden)

    Poirier M.

    2013-11-01

    Full Text Available The 2p − nd absorption structures in medium Z elements present a valuable benchmark for atomic models since they exhibit a complex dependence on temperature and density. For these transitions lying in the X-ray range, one observes a competition between the spin-orbit splitting and the broadening associated to the excitation of complex structures. Detailed opacity codes based on the HULLAC or FAC suites agree with the statistical code SCO; but in iron computations predict higher peak absorption than measured. An addition procedure on opacities calculated with detailed codes is proposed and successfully tested.

  11. Vibrational analysis of various irotopes of L-alanyl-L-alanine in aqueous solution: Vibrational Absorption (VA), Vibrational Circular Dichroism (VCD), Raman and Raman Optical Activity (ROA) Spectra

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Nieminen, R.M.; Knapp-Mohammady, M.

    2003-01-01

    . DFT Becke3LYP/6-31G* theory has been used to determine the geometry, Hessian, atomic polar tensors (APT), and atomic axial tensors (AAT), and the electric dipole-electric dipole polarizability derivatives (EDEDPD), which are required for us to simulate the VA, VCD, and Raman spectra. The electric...

  12. UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298-K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Ellermann, T.; Bartkiewicz, E.

    1992-01-01

    The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm....... The measured cross section near the absorption maximum was sigma(CHF2O2)(240 nm) = (2.66 +/- 0.46) x 10(-18) cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 --> products, defined as d[R]/dt = 2k(1obs)[CHF2O2]2, k(1......obs) = (5.0 +/- 0.7) x 10(-12) cm3 molecule-1 s-1 (+/- 2-sigma). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals....

  13. Crystal field splitting and spin states of Co ions in cobalt ferrite with composition Co{sub 1.5}Fe{sub 1.5}O{sub 4} using magnetization and X-ray absorption spectroscopy measurements

    Energy Technology Data Exchange (ETDEWEB)

    Sinha, A.K., E-mail: anil@rrcat.gov.in [HXAL, Synchrotrons Utilization Section, RRCAT, Indore 452013 (India); Homi Bhabha National Institute, RRCAT, Indore 452013 (India); Singh, M.N. [HXAL, Synchrotrons Utilization Section, RRCAT, Indore 452013 (India); Achary, S.N. [Chemistry Division, BARC, Anushaktinagar, Mumbai 400085 (India); Sagdeo, A. [HXAL, Synchrotrons Utilization Section, RRCAT, Indore 452013 (India); Homi Bhabha National Institute, RRCAT, Indore 452013 (India); Shukla, D.K.; Phase, D.M. [UGC-DAE Consortium for Scientific Research, Indore 452010 (India)

    2017-08-01

    Highlights: • Co ions in Co{sub 1.5}Fe{sub 1.5}O{sub 4} are found to be in high spin states. • XAS measurements have been used to estimate TM crystal field and core hole contributions to 3d orbital splitting. • The polycrystalline Co{sub 1.5}Fe{sub 1.5}O{sub 4} sample show two pinning centers and large magneto crystalline anisotropy. - Abstract: Structural, magnetic and electronic properties of partially inverted Cobalt Ferrite with composition Co{sub 1.5}Fe{sub 1.5}O{sub 4} 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 (T{sub H}) and octahedral (O{sub H}) sites. Spin states of Co{sup 3+} ions in T{sub H} 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 L{sub 2,3}-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 t{sub 2g} and e{sub g} absorption bands in O-K edge XAS spectrum is used to estimate the spin states of Co ions at O{sub H} and T{sub H} sites. The results are in agreement with those obtained from magnetization data, and favors Co{sup 3+} ions in T{sub H} sites in high spin states. Normalized areas of the satellite peaks in TM L{sub 2},{sub 3}-edge XAS spectra have been used to estimate 3d{sub n+1}L contribution in ground state wave function and the contributions were found to be significant.

  14. A PEM fuel cell for in situ XAS studies

    International Nuclear Information System (INIS)

    Wiltshire, Richard J.K.; King, Colin R.; Rose, Abigail; Wells, Peter P.; Hogarth, Martin P.; Thompsett, David; Russell, Andrea E.

    2005-01-01

    A miniature proton exchange membrane (PEM) fuel cell has been designed to enable in situ XAS investigations of the anode catalyst using fluorescence detection. The development of the cell is described, in particular the modifications required for elevated temperature operation and humidification of the feed gasses. The impact of the operating conditions is observed as an increase in the catalyst utilisation, which is evident in the EXAFS collected at the Pt L III and Ru K edges for a PtRu/C catalyst. The Pt component of the catalyst was found to be readily reduced by hydrogen in the fuel, while the Ru was only fully reduced under conditions of good gas flow and electrochemical contact. Under such conditions no evidence of O neighbours were found at the Ru edge. The results are interpreted in relation to the lack of surface sensitivity of the EXAFS method and indicate that the equilibrium coverage of O species on the Ru surface sites is too low to be observed using EXAFS

  15. Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

    Science.gov (United States)

    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).

  16. X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

    Energy Technology Data Exchange (ETDEWEB)

    McKeown, David A., E-mail: davidm@vsl.cua.edu; Gan, Hao; Pegg, Ian L.

    2017-05-15

    Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo{sup 6+}O{sub 4} with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V{sup 5+}O{sub 4} as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν{sub 1}) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm{sup −1} for glasses that change from Li{sup +} to Na{sup +} as the dominant network-modifying species. This indicates that MoO{sub 4} tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na{sup +} and Li{sup +}. Secondary ν{sub 1} frequency effects, with changes up to 7 cm{sup −1}, were also observed with increasing V{sub 2}O{sub 5} and MoO{sub 3} content. These secondary trends may indicate MoO{sub 4}-MoO{sub 4} and MoO{sub 4}-VO{sub 4} clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation. - Highlights: •Raman and XAS data indicate isolated MoO{sub 4} tetrahedra from the borosilicate network. •Mo-O stretch frequency is sensitive to network-modifying Li and Na concentrations. •Mo-O stretch frequency shifts were also seen with increasing V{sub 2}O{sub 5} and MoO{sub 3} content. •The Raman trends may indicate MoO{sub 4}-MoO{sub 4} and MoO{sub 4}-VO{sub 4} clustering in the glass. •V may stabilize Mo in the glass matrix avoiding yellow phase formation.

  17. Optically detected X-ray absorption spectroscopy measurements as a means of monitoring corrosion layers on copper.

    Science.gov (United States)

    Dowsett, Mark G; Adriaens, Annemie; Jones, Gareth K C; Poolton, Nigel; Fiddy, Steven; Nikitenko, Sergé

    2008-11-15

    XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. Where the near-visible photons have a shorter range in a material, the data will be more surface specific. Moreover, optical radiation may escape more readily than X-rays through liquid in an environmental cell. Here, we describe a first test of optically detected X-ray absorption spectroscopy (ODXAS) for monitoring electrochemical treatments on copper-based alloys, for example, heritage metals. Artificially made corrosion products deposited on a copper substrate were analyzed in air and in a 1% (w/v) sodium sesquicarbonate solution to simulate typical conservation methods for copper-based objects recovered from marine environments. The measurements were made on stations 7.1 and 9.2 MF (SRS Daresbury, UK) using the mobile luminescence end station (MoLES), supplemented by XAS measurements taken on DUBBLE (BM26 A) at the ESRF. The ODXAS spectra usually contain fine structure similar to that of XAS spectra measured in X-ray fluorescence. Importantly, for the compounds examined, the ODXAS is significantly more surface specific, and >98% characteristic of thin surface layers of 0.5-1.5-microm thickness in cases where X-ray measurements are dominated by the substrate. However, EXAFS and XANES from broadband optical measurements are superimposed on a high background due to other optical emission modes. This produces statistical fluctuations up to double what would be expected from normal counting statistics because the data retain the absolute statistical fluctuation in the original raw count, while losing up to 70% of their magnitude when background is removed. The problem may be

  18. Extragalactic Background Light expected from photon-photon absorption on spectra of Active Galactic Nuclei at distances from z=0.018 to z=1.375

    International Nuclear Information System (INIS)

    Sinitsyna, V Y; Sinitsyna, V G

    2013-01-01

    Extragalactic background radiation blocks the propagation of TeV gamma-ray over large distances by producing e + e − pairs. As a result, primary spectrum of gamma-source is changed, depending on spectrum of background light. So, hard spectra of Active Galactic Nuclei with high red shifts allow the determination of a EBL spectrum. The redshifts of SHALON TeV gamma-ray sources range from 0.018 to 1.375 those spectra are resolved at the energies from 800 GeV to about 50 TeV. Spectral energy distribution of EBL constrained from observations of Mkn421, Mkn501, Mkn180, OJ287, 3c454.3 and 1739+522 together with models and measurements are presented.

  19. Ionization yield and absorption spectra reveal superexcited Rydberg state relaxation processes in H{sub 2}O and D{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Fillion, J-H [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Dulieu, F [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Baouche, S [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Lemaire, J-L [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France); Jochims, H W [Institut fuer Physikalische und Theoretische Chemie der Freien Universitaet Berlin, Takustrasse 3, D-14195 Berlin 33 (Germany); Leach, S [LERMA, CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 place J Janssen, F-92195, Meudon (France)

    2003-07-14

    The absorption cross section and the ionization quantum yield of H{sub 2}O have been measured using a synchrotron radiation source between 9 and 22 eV. Comparison between the two curves highlights competition between relaxation processes for Rydberg states converging to the first A-tilde {sup 2}A{sub 1} and to the second B-tilde {sup 2}B{sub 2} excited states of H{sub 2}O{sup +}. Comparison with D{sub 2}O absorption and ionization yields, derived from Katayama et al (1973 J. Chem. Phys. 59 4309), reveals specific energy-dependent deuteration effects on competitive predissociation and autoionization relaxation channels. Direct ionization was found to be only slightly affected by deuteration.

  20. Theoretical and experimental study of high-magnetic-field XMCD spectra at the L2,3 absorption edges of mixed-valence rare-earth compounds

    International Nuclear Information System (INIS)

    Kotani, Akio; Matsuda, Yasuhiro H; Nojiri, Hiroyuki

    2009-01-01

    X-ray magnetic circular dichroism(XMCD) spectra at the L 2,3 edges of mixed-valence rare-earth compounds in high magnetic fields are studied both theoretically and experimentally. The theoretical study is based on a new framework proposed recently by Kotani. The Zeeman splitting of 4f states, the mixed-valence character of 4f states, and the 4f-5d exchange interaction are incorporated into a single impurity Anderson model. New XMCD experiments in high magnetic fields up to 40 T are carried out for the mixed-valence compounds EuNi 2 (Si 0.18 Ge 0.82 ) 2 and YbInCu 4 by using a miniature pulsed magnet, which was developed recently by Matsuda et al. The XMCD data are taken at 5 K by transmission measurements for incident X-rays with ± helicities at BL39XU in SPring-8. After giving a survey on recent developments in the theory of XMCD spectra for mixed-valence Ce and Yb compounds, we calculate the XMCD spectra of YbInCu 4 at the field-induced valence transition around 32 T by applying the recent theoretical framework and by newly introducing at 32 T a discontinuous change in the Yb 4f level and that in the hybridization strength between the Yb 4f and conduction electrons. The calculated results are compared with the experimental ones.

  1. Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials

    Energy Technology Data Exchange (ETDEWEB)

    Verma, Prakash; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu [Quantum Theory Project, University of Florida, Gainesville, Florida 32611 (United States)

    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.

  2. Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

    Science.gov (United States)

    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.

  3. Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

    Science.gov (United States)

    Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

    2017-07-18

    Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

  4. Photobleaching Response of Different Sources of Chromophoric Dissolved Organic Matter Exposed to Natural Solar Radiation Using Absorption and Excitation?Emission Matrix Spectra

    OpenAIRE

    Zhang, Yunlin; Liu, Xiaohan; Osburn, Christopher L.; Wang, Mingzhu; Qin, Boqiang; Zhou, Yongqiang

    2013-01-01

    CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrea...

  5. An in-situ X-ray absorption spectroelectrochemical study of the electroreduction of uranium ions in HCl, HNO{sub 3}, and Na{sub 2}CO{sub 3} solutions

    Energy Technology Data Exchange (ETDEWEB)

    Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu [Kyoto Univ., Osaka (Japan). Div. of Nuclear Engineering Science; Okamoto, Yoshihiro [Japan Atomic Energy Agency, Ibaraki (Japan). Quantum Beam Science Directorate

    2016-04-01

    A spectroelectrochemical cell was fabricated for in-situ X-ray absorption spectroscopy (in-situ XAS). The XAS spectra of the uranium L{sub III} edge were monitored in electrolyte solutions during the electrochemical reduction. Tetravalent uranium, U{sup 4+}, in 1 mol dm{sup -3} (M) hydrochloric acid (HCl) was electrochemically prepared from hexavalent uranium, UO{sub 2}{sup 2+}, by constant current electrolysis, and the extended X-ray absorption fine structure (EXAFS) was analyzed. The concentration ratio of UO{sub 2}{sup 2+} and U{sup 4+}, which were formed via the disproportionation of pentavalent uranium, UO{sub 2}{sup +}, during the electrolysis, were calculated based on the intensity of the signal for the two axial oxygen atoms in the linear UO{sub 2}{sup 2+} unit, the U-O{sub ax}, bond that had a radial structural function. The apparent redox potential of the UO{sub 2}{sup 2+}/U{sup 4+} couple in 1 M HCl was determined based on the Nernst equation using the concentrations of UO{sub 2}{sup 2+} and U{sup 4+}. The electrode potential was shown to be close to the formal potential of the UO{sub 2}{sup 2+}/UO{sub 2}{sup +} couple as reported previously. This result indicates that the UO{sub 2}{sup +} that was formed electrochemically at the electrode disproportionated to form UO{sub 2}{sup 2+} and U{sup 4+} in the bulk solution. The in-situ XAS of UO{sub 2}{sup 2+} in 0.1 M nitric acid was also performed. The U{sup 4+} that formed was partially re-oxidized to UO{sub 2}{sup 2+} by the NO{sub 3}{sup -} present in the solution. The formation of the UO{sub 2}{sup +} carbonato complex was observed by in-situ XAS in a 1 M sodium carbonate solution during the bulk electrolysis. The edge jump of the X-ray absorption near edge structure (XANES) spectrum shifted from 17.164 to 17.163 keV, and the bond distances of U-O{sub ax} and U-O for CO{sub 3}{sup 2-} increased from 1.78 to 1.88 Aa and from 2.42 to 2.53 Aa, respectively, because of the reduction of the UO{sub 2}{sup 2

  6. Ancient wood of the Acqualadrone rostrum: materials history through gas chromatography/mass spectrometry and sulfur X-ray absorption spectroscopy.

    Science.gov (United States)

    Frank, Patrick; Caruso, Francesco; Caponetti, Eugenio

    2012-05-15

    In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge X-ray absorption spectroscopy (XAS) and gas chromatography/mass spectrometry (GC/MS). GC/MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic (dimethylsulfonio)propionate. High-valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality.

  7. The Ancient Wood of the Acqualadrone Rostrum: A Materials History Through GC-MS and Sulfur X-ray Absorption Spectroscopy

    Science.gov (United States)

    Frank, Patrick; Caruso, Francesco; Caponetti, Eugenio

    2012-01-01

    In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge x-ray absorption spectroscopy (XAS) and GC-MS. GC-MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic dimethylsulfonio-propionate. High valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality. PMID:22545724

  8. Variations in the spectral values of specific absorption of phytoplankton

    Digital Repository Service at National Institute of Oceanography (India)

    Sathyendranath, S.; Lazzara, L.; Prieur, L.

    Absorption spectra of laboratory cultures of eight species of phytoplankton were studied. These spectra, normalized per unit of chlorophyll a concentration (specific absorption) show variability in magnitude and spectral form. Specific absorption...

  9. High-resolution Al L2,3-edge x-ray absorption near edge structure spectra of Al-containing crystals and glasses: coordination number and bonding information from edge components

    International Nuclear Information System (INIS)

    Weigel, C; Calas, G; Cormier, L; Galoisy, L; Henderson, G S

    2008-01-01

    High-resolution Al L 2,3 -edge x-ray absorption near edge structure (XANES) spectra have been measured in selected materials containing aluminium in 4-, 5- and 6-coordination. A shift of 1.5 eV is observed between the onset of [4] Al and [6] Al L 2,3 -edge XANES, in agreement with the magnitude of the shift observed at the Al K-edge. The differences in the position and shape of low-energy components of Al L 2,3 -edge XANES spectra provide a unique fingerprint of the geometry of the Al site and of the nature of Al-O chemical bond. The high resolution allows the calculation of electronic parameters such as the spin-orbit coupling and exchange energy using intermediate coupling theory. The electron-hole exchange energy decreases in tetrahedral as compared to octahedral symmetry, in relation with the increased screening of the core hole in the former. Al L 2,3 -edge XANES spectra confirm a major structural difference between glassy and crystalline NaAlSi 2 O 6 , with Al in 4- and 6-coordination, respectively, Al coordination remaining unchanged in NaAl 1-x Fe x Si 2 O 6 glasses, as Fe is substituted for Al

  10. X-ray Absorption Spectroscopy in Mineralogy: A Review

    International Nuclear Information System (INIS)

    Mottana, Annibale

    2003-01-01

    The number of mineral species known to date rapidly approaches 4000, and yet they represent but a small fraction of all the known inorganic and organic compounds. Nevertheless, minerals represent an ideal field of activity for X-ray absorption spectroscopy (XAS), because the investigation of their crystal-chemical peculiarities takes an enormous advantage of the property of this method of being atom-selective, even in the presence of a wide range of competing atoms located in similar structural environments. As a matter of fact, XAS on minerals proved to be a useful probing method as early as for W. Kossel's pioneer studies of in the 1930's, just after the fine structures occurring at and near the absorption edge had been first detected. However, XAS did not really become consolidated in mineral studies until the 1980's, when synchrotron sources became available to users. A concise, but complete review of the historical and recent applications of XAS to minerals and to their analogues synthesized for geological/geophysical purposes i.e., to better understand the mechanisms by which the Earth evolves, is here given. Special reference will be made to transition metals (Ca, Ti, Cr, Mn, Fe, Ni) which absorb in the hard X-ray spectral region (> 4 KeV) and to the geologically-significant elements (O, Na, Mg, Al, Si, S and K) which absorb in the soft X-ray region (500-4000 eV)

  11. Atmospheric lifetimes, infrared absorption spectra, radiative forcings and global warming potentials of NF3 and CF3CF2Cl (CFC-115

    Directory of Open Access Journals (Sweden)

    A. Totterdill

    2016-09-01

    Full Text Available Fluorinated compounds such as NF3 and C2F5Cl (CFC-115 are characterised by very large global warming potentials (GWPs, which result from extremely long atmospheric lifetimes and strong infrared absorptions in the atmospheric window. In this study we have experimentally determined the infrared absorption cross sections of NF3 and CFC-115, calculated the radiative forcing and efficiency using two radiative transfer models and identified the effect of clouds and stratospheric adjustment. The infrared cross sections are within 10 % of previous measurements for CFC-115 but are found to be somewhat larger than previous estimates for NF3, leading to a radiative efficiency for NF3 that is 25 % larger than that quoted in the Intergovernmental Panel on Climate Change Fifth Assessment Report. A whole atmosphere chemistry–climate model was used to determine the atmospheric lifetimes of NF3 and CFC-115 to be (509 ± 21 years and (492 ± 22 years, respectively. The GWPs for NF3 are estimated to be 15 600, 19 700 and 19 700 over 20, 100 and 500 years, respectively. Similarly, the GWPs for CFC-115 are 6030, 7570 and 7480 over 20, 100 and 500 years, respectively.

  12. Experimental and theoretical studies of the VUV emission and absorption spectra of H{sub 2}, HD and D{sub 2} molecules; Etude experimentale et theorique des spectres d'emission et d'absorption VUV des molecules H{sub 2}, D{sub 2} et HD

    Energy Technology Data Exchange (ETDEWEB)

    Roudjane, M

    2007-12-15

    The aim of this thesis is to carry out an experimental study of the absorption and emission spectra of the D{sub 2} and HD isotopes, with high resolution, in the VUV domain and to supplement it by a theoretical study of the excited electronic states involved in the observed transitions. The emission spectra of HD and D{sub 2} are produced by Penning discharge source operating under low pressure and are recorded in the spectral range 78 - 170 nm. The recorded spectra contains more than 20.000 lines. The analysis of the spectrum consists in identifying and assigning the lines to the electronic transitions between energy levels of the molecule. The present analysis is based on our theoretical calculations of the ro-vibrational energy levels of the excited electronic states and the transition probabilities from these states towards the energy levels of the fundamental state. The theoretical results are obtained by resolving the coupled equations between the excited electronic states B{sup 1}{sigma}{sub u}{sup 1}, B'{sup 1}{sigma}{sub u}{sup 1}, C{sup 1}{pi}{sub u}{sup 1} and D{sup 1}{pi}{sub u}{sup 1}, taking into account the nonadiabatic couplings between these states, and they are obtained in the adiabatic approximation for the excited electronic states B''B-bar{sup 1}{sigma}{sub u}{sup +}, D'{sup 1}{pi}{sub u}{sup 1} and D''{sup 1}{pi}{sub u}{sup 1}. The equations are resolved using a modern method based on the discretization variables representation method. In addition, we have carried out a study of the absorption spectra of the HD and D{sub 2} molecules.

  13. Absorption spectra between 0.8 {mu} and 30 {mu} of mixtures of H{sub 2}O - D{sub 2}O in the liquid state; Le spectre d'absorption des melanges H{sub 2}O-D{sub 2}O a l'etat liquide entre 0,8 et 30 {mu}

    Energy Technology Data Exchange (ETDEWEB)

    Ceccaldi, M; Goldman, M; Roth, E [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    There has been very little work carried out recently on the absorption bands of H{sub 2}O, HDO and D{sub 2}O in the liquid state. We have established the spectra of these molecules in between 0.8 and 30 p. The table of absorption bands of the molecules HDO and D{sub 2}O for which all the bands corresponding to those for H{sub 2}O had not been established has been completed. We have sought a convenient method of representing the variations in optical density of certain HDO bands as a function of the concentration of heavy water in the mixtures studied. (author) [French] Il y a peu de travaux recents sur les bandes d'absorption de H{sub 2}O, HDO et D{sub 2}O a l'etat liquide. Nous avons releve les spectres de ces molecules entre 0,8 et 30 p. Le tableau des bandes d'absorption des molecules HDO et D{sub 2}O, pour lesquelles le releve de toutes les bandes correspondantes a celles de H{sub 2}O n'etait pas encore effectue, a ete complete. Nous avons cherche des modes de representation commodes des variations de densite optique de certaines bandes de HDO en fonction de la teneur en eau lourde des melanges etudies. (auteur)

  14. Photobleaching response of different sources of chromophoric dissolved organic matter exposed to natural solar radiation using absorption and excitation-emission matrix spectra.

    Science.gov (United States)

    Zhang, Yunlin; Liu, Xiaohan; Osburn, Christopher L; Wang, Mingzhu; Qin, Boqiang; Zhou, Yongqiang

    2013-01-01

    CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrease in total dissolved nitrogen (TDN) concentration under natural sunlight exposure for both WDA and PDA CDOM, indicating photoproduction of ammonium from TDN. In contrast, photobleaching caused a marked increase in total dissolved phosphorus (TDP) concentration for both WDA and PDA CDOM. Thus TDN:TDP ratios decreased significantly both for WDA and PDA CDOM, which partially explained the seasonal dynamic of TDN:TDP ratio in Lake Taihu. Photobleaching rate of CDOM absorption a(254), was 0.032 m/MJ for WDA CDOM and 0.051 m/MJ for PDA CDOM from days 0-9, indicating that phototransformations were initially more rapid for the newly produced CDOM from phytoplankton than for the river CDOM. Extrapolation of these values to the field indicated that 3.9%-5.1% CDOM at the water surface was photobleached and mineralized every day in summer in Lake Taihu. Photobleaching caused the increase of spectral slope, spectral slope ratio and molecular size, indicating the CDOM mean molecular weight decrease which was favorable to further microbial degradation of mineralization. Three fluorescent components were validated in parallel factor analysis models calculated separately for WDA and PDA CDOM. Our study suggests that the humic-like fluorescence materials could be rapidly and easily photobleached for WDA and PDA CDOM, but the protein-like fluorescence materials was not photobleached and even increased from the transformation of the humic-like fluorescence substance to the protein

  15. Opacity of iron, nickel, and copper plasmas in the x-ray wavelength range: Theoretical interpretation of 2p-3d absorption spectra

    International Nuclear Information System (INIS)

    Blenski, T.; Loisel, G.; Poirier, M.; Thais, F.; Arnault, P.; Caillaud, T.; Fariaut, J.; Gilleron, F.; Pain, J.-C.; Porcherot, Q.; Reverdin, C.; Silvert, V.; Villette, B.; Bastiani-Ceccotti, S.; Turck-Chieze, S.; Foelsner, W.; Gaufridy de Dortan, F. de

    2011-01-01

    This paper deals with theoretical studies on the 2p-3d absorption in iron, nickel, and copper plasmas related to LULI2000 (Laboratoire pour l'Utilisation des Lasers Intenses, 2000J facility) measurements in which target temperatures were of the order of 20 eV and plasma densities were in the range 0.004-0.01 g/cm 3 . The radiatively heated targets were close to local thermodynamic equilibrium (LTE). The structure of 2p-3d transitions has been studied with the help of the statistical superconfiguration opacity code sco and with the fine-structure atomic physics codes hullac and fac. A new mixed version of the sco code allowing one to treat part of the configurations by detailed calculation based on the Cowan's code rcg has been also used in these comparisons. Special attention was paid to comparisons between theory and experiment concerning the term features which cannot be reproduced by sco. The differences in the spin-orbit splitting and the statistical (thermal) broadening of the 2p-3d transitions have been investigated as a function of the atomic number Z. It appears that at the conditions of the experiment the role of the term and configuration broadening was different in the three analyzed elements, this broadening being sensitive to the atomic number. Some effects of the temperature gradients and possible non-LTE effects have been studied with the help of the radiative-collisional code scric. The sensitivity of the 2p-3d structures with respect to temperature and density in medium-Z plasmas may be helpful for diagnostics of LTE plasmas especially in future experiments on the Δn=0 absorption in medium-Z plasmas for astrophysical applications.

  16. Ab Initio Potential Energy Surfaces for Both the Ground (X̃1A′ and Excited (A∼1A′′ Electronic States of HSiBr and the Absorption and Emission Spectra of HSiBr/DSiBr

    Directory of Open Access Journals (Sweden)

    Anyang Li

    2012-01-01

    Full Text Available Ab initio potential energy surfaces for the ground (X̃1A′ and excited (A˜A′′1 electronic states of HSiBr were obtained by using the single and double excitation coupled-cluster theory with a noniterative perturbation treatment of triple excitations and the multireference configuration interaction with Davidson correction, respectively, employing an augmented correlation-consistent polarized valence quadruple zeta basis set. The calculated vibrational energy levels of HSiBr and DSiBr of the ground and excited electronic states are in excellent agreement with the available experimental band origins. In addition, the absorption and emission spectra of HSiBr and DSiBr were calculated using an efficient single Lanczos propagation method and are in good agreement with the available experimental observations.

  17. Photobleaching Response of Different Sources of Chromophoric Dissolved Organic Matter Exposed to Natural Solar Radiation Using Absorption and Excitation–Emission Matrix Spectra

    Science.gov (United States)

    Zhang, Yunlin; Liu, Xiaohan; Osburn, Christopher L.; Wang, Mingzhu; Qin, Boqiang; Zhou, Yongqiang

    2013-01-01

    CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrease in total dissolved nitrogen (TDN) concentration under natural sunlight exposure for both WDA and PDA CDOM, indicating photoproduction of ammonium from TDN. In contrast, photobleaching caused a marked increase in total dissolved phosphorus (TDP) concentration for both WDA and PDA CDOM. Thus TDN∶TDP ratios decreased significantly both for WDA and PDA CDOM, which partially explained the seasonal dynamic of TDN∶TDP ratio in Lake Taihu. Photobleaching rate of CDOM absorption a(254), was 0.032 m/MJ for WDA CDOM and 0.051 m/MJ for PDA CDOM from days 0–9, indicating that phototransformations were initially more rapid for the newly produced CDOM from phytoplankton than for the river CDOM. Extrapolation of these values to the field indicated that 3.9%–5.1% CDOM at the water surface was photobleached and mineralized every day in summer in Lake Taihu. Photobleaching caused the increase of spectral slope, spectral slope ratio and molecular size, indicating the CDOM mean molecular weight decrease which was favorable to further microbial degradation of mineralization. Three fluorescent components were validated in parallel factor analysis models calculated separately for WDA and PDA CDOM. Our study suggests that the humic-like fluorescence materials could be rapidly and easily photobleached for WDA and PDA CDOM, but the protein-like fluorescence materials was not photobleached and even increased from the transformation of the humic-like fluorescence substance to the protein

  18. X-ray Absorption Spectroscopy Combined with Time-Dependent Density Functional Theory Elucidates Differential Substitution Pathways of Au(I) and Au(III) with Zinc Fingers.

    Science.gov (United States)

    Abbehausen, Camilla; de Paiva, Raphael Enoque Ferraz; Bjornsson, Ragnar; Gomes, Saulo Quintana; Du, Zhifeng; Corbi, Pedro Paulo; Lima, Frederico Alves; Farrell, Nicholas

    2018-01-02

    A combination of two elements' (Au, Zn) X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TD-DFT) allowed the elucidation of differential substitution pathways of Au(I) and Au(III) compounds reacting with biologically relevant zinc fingers (ZnFs). Gold L 3 -edge XAS probed the interaction of gold and the C-terminal Cys 2 HisCys finger of the HIV-1 nucleocapsid protein NCp7, and the Cys 2 His 2 human transcription factor Sp1. The use of model compounds helped assign oxidation states and the identity of the gold-bound ligands. The computational studies accurately reproduced the experimental XAS spectra and allowed the proposition of structural models for the interaction products at early time points. The direct electrophilic attack on the ZnF by the highly thiophilic Au(I) resulted in a linear P-Au-Cys coordination sphere after zinc ejection whereas for the Sp1, loss of PEt 3 results in linear Cys-Au-Cys or Cys-Au-His arrangements. Reactions with Au(III) compounds, on the other hand, showed multiple binding modes. Prompt reaction between [AuCl(dien)] 2+ and [Au(dien)(DMAP)] 3+ with Sp1 showed a partially reduced Au center and a final linear His-Au-His coordination. Differently, in the presence of NCp7, [AuCl(dien)] 2+ readily reduces to Au(I) and changes from square-planar to linear geometry with Cys-Au-His coordination, while [Au(dien)(DMAP)] 3+ initially maintains its Au(III) oxidation state and square-planar geometry and the same first coordination sphere. The latter is the first observation of a "noncovalent" interaction of a Au(III) complex with a zinc finger and confirms early hypotheses that stabilization of Au(III) occurs with N-donor ligands. Modification of the zinc coordination sphere, suggesting full or partial zinc ejection, is observed in all cases, and for [Au(dien)(DMAP)] 3+ this represents a novel mechanism for nucleocapsid inactivation. The combination of XAS and TD-DFT presents the first direct experimental

  19. Physical aspects of relaxation and shake-up effects in XPS and core →2π* absorption spectra of CO chemisorbed on Ni (111)

    International Nuclear Information System (INIS)

    Gumhalter, B.

    1985-07-01

    The physical origin of the peculiar relaxation shifts and spectral shapes appearing in x-ray induced core-to-valence excitation and core level photoemission spectra of CO chemisorbed on Ni(111) are discussed and interpreted within a unique framework. Within the model presented the electronic transitions in core-to-valence excitation spectroscopy and XPS are shown to give rise to drastic electronic rearrangements within the adsorption system and to the charge shake-up in the CO 2π* derived resonance partly filled via the backdonation mechanism. Such singular relaxation processes, common to both spectroscopies, are closely related and can be treated on the same footing. This makes possible to establish unique relaxation shifts and spectral characteristics for two seemingly different experimental situations. The use of this formalism in analysing the experimental data enables one to estimate and distinguish between the extra-adsorbate (image or nonbonding) and intra-adsorbate (chemically induced) screening of the core holes created either by x-ray induced core-to-valence electronic transitions or core level photoionization in CO/Ni(111). (author)

  20. Erratum: "Photoionization Modeling of Oxygen K Absorption in the Interstellar Medium, the Chandra Grating Spectra of XTE J1817-330" (2013, Apj, 768, 60)

    Science.gov (United States)

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

    2013-01-01

    In the published version of this paper, there are some minor inaccuracies in the absorption-line wavelengths listed in Table 4 as a result of a faulty reduction procedure of the Obs6615 spectrum. The shifts have been detected in a comparison with the wavelengths listed for this spectrum in the Chandra Transmission Grating Catalog and Archive (TGCat8). They are due to incorrect centroid positions of the zero-order image in both reductions as determined by the tgdetect utility which, when disentangled, yield the improved line positions of the amended Table 4 given below. It must also be pointed out that other quantitative findings of the original paper: 1. Table 5, p. 9: the column density (NH), ionization parameter, oxygen abundance of the warmabs model and the normalization and photon index of the power-law model; 2. Table 6, p. 9: the hydrogen column density of the warmabs fit; 3. Table 7, p. 9: the present oxygen equivalent widths of XTE J1817-330; and 4. Table 8, p. 10: the present oxygen column densities of XTE J1817-330 derived from both the curve of growth and warmabs model fit have been revised in the new light and are, within the estimated uncertainty ranges, in good accord with the new rendering.

  1. Power and polarization dependences of ultra-narrow electromagnetically induced absorption (EIA) spectra of 85 Rb atoms in degenerate two-level system

    Science.gov (United States)

    Qureshi, Muhammad Mohsin; Rehman, Hafeez Ur; Noh, Heung-Ryoul; Kim, Jin-Tae

    2016-05-01

    We have investigated ultra-narrow EIA spectral features with respect to variations of polarizations and powers of pump laser beam in a degenerate two-level system of the transition of 85 Rb D2 transition line. Polarizations of the probe laser beam in two separate experiments were fixed at right circular and horizontal linear polarizations, respectively while the polarizations of the pump lasers were varied from initial polarizations same as the probe laser beams to orthogonal to probe polarizations. One homemade laser combined with AOMs was used to the pump and probe laser beams instead of two different lasers to overcome broad linewidths of the homemade lasers. Theoretically, probe absorption coefficients have been calculated from optical Bloch equations of the degenerate two level system prepared by a pump laser beam. In the case of the circular polarization, EIA signal was obtained as expected theoretically although both pump and probe beams have same polarization. The EIA signal become smaller as power increases and polarizations of the pump and probe beams were same. When the polarization of the pump beam was linear polarization, maximum EIA signal was obtained theoretically and experimentally. Experimental EIA spectral shapes with respect to variations of the pump beam polarization shows similar trends as the theoretical results.

  2. X-ray absorption study of silicon carbide thin film deposited by pulsed laser deposition

    International Nuclear Information System (INIS)

    Monaco, G.; Suman, M.; Garoli, D.; Pelizzo, M.G.; Nicolosi, P.

    2011-01-01

    Silicon carbide (SiC) is an important material for several applications ranging from electronics to Extreme UltraViolet (EUV) space optics. Crystalline cubic SiC (3C-SiC) has a wide band gap (near 2.4 eV) and it is a promising material to be used in high frequency and high energetic electronic devices. We have deposited, by means of pulsed laser deposition (PLD), different SiC films on sapphire and silicon substrates both at mild (650 o C) and at room temperature. The resulted films have different structures such as: highly oriented polycrystalline, polycrystalline and amorphous which have been studied by means of X-ray absorption spectroscopy (XAS) near the Si L 2,3 edge and the C K edge using PES (photoemission spectroscopy) for the analysis of the valence bands structure and film composition. The samples obtained by PLD have shown different spectra among the grown films, some of them showing typical 3C-SiC absorption structure, but also the presence of some Si-Si and graphitic bonds.

  3. Room temperature redox reaction by oxide ion migration at carbon/Gd-doped CeO2 heterointerface probed by an in situ hard x-ray photoemission and soft x-ray absorption spectroscopies

    Directory of Open Access Journals (Sweden)

    Takashi Tsuchiya, Shogo Miyoshi, Yoshiyuki Yamashita, Hideki Yoshikawa, Kazuya Terabe, Keisuke Kobayashi and Shu Yamaguchi

    2013-01-01

    Full Text Available In situ hard x-ray photoemission spectroscopy (HX-PES and soft x-ray absorption spectroscopy (SX-XAS have been employed to investigate a local redox reaction at the carbon/Gd-doped CeO2 (GDC thin film heterointerface under applied dc bias. In HX-PES, Ce3d and O1s core levels show a parallel chemical shift as large as 3.2 eV, corresponding to the redox window where ionic conductivity is predominant. The window width is equal to the energy gap between donor and acceptor levels of the GDC electrolyte. The Ce M-edge SX-XAS spectra also show a considerable increase of Ce3+ satellite peak intensity, corresponding to electrochemical reduction by oxide ion migration. In addition to the reversible redox reaction, two distinct phenomena by the electrochemical transport of oxide ions are observed as an irreversible reduction of the entire oxide film by O2 evolution from the GDC film to the gas phase, as well as a vigorous precipitation of oxygen gas at the bottom electrode to lift off the GDC film. These in situ spectroscopic observations describe well the electrochemical polarization behavior of a metal/GDC/metal capacitor-like two-electrode cell at room temperature.

  4. X-ray absorption spectroscopy study of the LixFePO4 cathode during cycling using a novel electrochemical in situ reaction cell

    International Nuclear Information System (INIS)

    Deb, A.; Bergmann, U.; Cairns, E.L.; California Univ., Berkeley, CA; Cramer, S.P.; California Univ., Davis, CA

    2004-01-01

    The extraction and insertion of lithium in LiFePO 4 has been investigated in practical Li-ion intercalation electrodes for Li-ion batteries using Fe K-edge X-ray absorption spectroscopy (XAS). A versatile electrochemical in situ reaction cell was utilized, specifically designed for long-term X-ray experiments on battery electrodes during the lithium-extraction/insertion process in electrode materials for Li-ion batteries. The electrode contained about 7.7 mg of LiFePO 4 on a 20 μm-thick Al foil. In order to determine the charge compensation mechanism and structural perturbations occurring in the system during cycling, in situ X-ray absorption fine-structure spectroscopy (XAFS) measurements were conducted on the cell at a moderate rate using typical Li-ion battery operating voltages (3.0-4.1 V versus Li/Li + ).XAS studies of the LiFePO 4 electrode measured at the initial state (LiFePO 4 ) showed iron to be in the Fe(II) state corresponding to the initial state (0.0 mAh) of the battery, whereas in the delithiated state (FePO 4 ) iron was found to be in the FE(III) state corresponding to the final charged state (3 m Ah) of the battery. The X-ray absorption near-edge structure (XANES) region of the XAS spectra revealed a high-spin configuration for the two states [Fe(II), d 6 and Fe(III), d 5 ]. The XAFS data analysis confirmed that the olivine structure of the LeFePO 4 and FePO 4 is retained by the electrodes, which is in agreement with the X-ray diffraction observations on these compounds. The XAFS data that were collected continuously during cycling revealed details about the response of the cathode to Li insertion and extraction. These measurements on the LiFePO 4 cathode show that the material retains good structural short-range order leading to superior cycling

  5. Coherent dynamics of interwell excitons in GaAs/AlxGa1-xAs superlattices

    DEFF Research Database (Denmark)

    Mizeikis, V.; Birkedal, Dan; Langbein, Wolfgang Werner

    1997-01-01

    Coherent exciton dynamics in a GaAs/AlxGa1-xAs narrow-miniband superlattice is studied by spectrally resolved transient four-wave mixing. Coherent optical properties of the investigated structure are found to be strongly affected by the existence of two different heavy-hole excitonic states. One...

  6. The structure of ZrO2 phases and deviltrification processes in a Ca-Zr-Si-O-based glass ceramic: a combined a-XRD and XAS study

    International Nuclear Information System (INIS)

    Meneghini, C.; Mobilio, S.

    2004-01-01

    The structure of Zr atomic environment in a CaO-ZrO 2 -Si 2 glass ceramic as a function of thermal treatments has been studied, combining X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD) and anomalous XRD (a-XRD) techniques. The analysis of XRD patterns demonstrates that the devitrification process proceeds through the partial segregation of Zr-depleted phases (wollastonite-like) and Zr-rich phases (Zr oxides). The XAS and a-XRD measurements at the Zr K-edge have been exploited in order to obtain a closer insight into the atomic structure around the Zr atoms. In the as-quenched glass the Zr atom is sixfold coordinated to O atoms in an amorphous environment rich in Ca and Si. Thermal treatment firstly (T=1273-1323 K) causes partial segragation of Zr in the form of an oxide with a tetragonal zirconia (t-ZrO 2 ) crystalline structure. Raising the temperature (T=1373 K) causes the formation of ZrO 2 crystallites in the monoclinic crystallographic phase (baddeleyite, m-ZrO 2 ). Analysis of the XAS data shows that a considerable amount of Zr remains in an amorphous calcium silicate phase. (orig.)

  7. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    International Nuclear Information System (INIS)

    Showalter, Allison R; Bunker, Bruce A; Szymanowski, Jennifer E S; Fein, Jeremy B

    2016-01-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense . This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense . The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values. (paper)

  8. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    Science.gov (United States)

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  9. A laser heating facility for energy-dispersive X-ray absorption spectroscopy

    DEFF Research Database (Denmark)

    Kantor, Innokenty; Marini, C.; Mathon, O.

    2018-01-01

    A double-sided laser heating setup for diamond anvil cells installed on the ID24 beamline of the ESRF is presented here. The setup geometry is specially adopted for the needs of energy-dispersive X-ray absorption spectroscopic (XAS) studies of materials under extreme pressure and temperature...... conditions. We illustrate the performance of the facility with a study on metallic nickel at 60 GPa. The XAS data provide the temperature of the melting onset and quantitative information on the structural parameters of the first coordination shell in the hot solid up to melting....

  10. FSFE: Fake Spectra Flux Extractor

    Science.gov (United States)

    Bird, Simeon

    2017-10-01

    The fake spectra flux extractor generates simulated quasar absorption spectra from a particle or adaptive mesh-based hydrodynamic simulation. It is implemented as a python module. It can produce both hydrogen and metal line spectra, if the simulation includes metals. The cloudy table for metal ionization fractions is included. Unlike earlier spectral generation codes, it produces absorption from each particle close to the sight-line individually, rather than first producing an average density in each spectral pixel, thus substantially preserving more of the small-scale velocity structure of the gas. The code supports both Gadget (ascl:0003.001) and AREPO.

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  13. XAS study of brownmillerites and Ruddlesden-Popper manganites

    International Nuclear Information System (INIS)

    Szczerba, W.; Oates, C.J.; Sikora, M.; Borowiec, M.; Kapusta, C.; Spalek, L.; Allix, M.; Rosseinsky, M.R.; Ruiz-Bustos, R.; Battle, P.D.

    2005-01-01

    X-Ray Absorption Spectroscopy study of selected compounds of the Ruddlesden-Popper and the browmillerite families is presented. Experiments were carried out at the beamline A1 in HASYLAB/DESY, Hamburg. The n = 1 and n = 2 compounds of the Ruddlesden Popper series, Sr 2 Mn 0.5 Ru 0.5 O 4 and Sr 3 MnRuO 7 as well as oxygen nonstoichiometric and gallium doped brownmillerite compounds, Ca 2.5 Sr 0.5 Ga 1+x Mn 2-x O 8- δ have been studied. Polycrystalline powder samples were measured at room temperature in transmission mode

  14. XAS characterisation of xenon bubbles in uranium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Martin, P. [CEA Cadarache, DEN/DEC/SESC/LLCC, Bat. 130, 13108 St. Paul Lez Durance (France)], E-mail: martinp@drncad.cea.fr; Garcia, P.; Carlot, G.; Sabathier, C.; Valot, C. [CEA Cadarache, DEN/DEC/SESC/LLCC, Bat. 130, 13108 St. Paul Lez Durance (France); Nassif, V. [CEA Grenoble, DSM/DRFMC/SP2M/NRS, 17 Avenue des Martyrs, 38054 Grenoble Cedex 9 (France); Proux, O. [Laboratoire de Geophysique Interne et Tectonophysique, UMR CNRS/Universite Joseph Fourier, 1381 rue de la Piscine, Domaine Universitaire, 38400 Saint-Martin-D' Heres (France); Hazemann, J.-L. [Institut Neel, CNRS, 25 Avenue des Martyrs, BP 166, 38042 Grenoble Cedex 9 (France)

    2008-06-15

    X-ray absorption spectroscopy experiments were performed on a set of uranium dioxide samples implanted with 10{sup 17} xenon cm{sup -2} at 800 keV (8 at.% at 140 nm). EXAFS measurements performed at 12 K showed that during implantation the gas forms highly pressurised nanometre size inclusions. Bubble pressures were estimated at 2.8 {+-} 0.3 GPa at low temperature. Following the low energy xenon implantation, samples were annealed between 1073 and 1773 K for several hours. Stability of nanometre size highly pressurized xenon aggregates in UO{sub 2} is demonstrated up to 1073 K as for this temperature almost no modification of the xenon environment was observed. Above this temperature, bubbles will trap migrating vacancies and their inner pressure is seen to decrease substantially.

  15. Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

    Science.gov (United States)

    Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

    2013-04-01

    The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data

  16. Electronic structures of GaAs/AlxGa1-xAs quantum double rings

    Directory of Open Access Journals (Sweden)

    Li Shu-Shen

    2006-01-01

    Full Text Available AbstractIn the framework of effective mass envelope function theory, the electronic structures of GaAs/AlxGa1-xAs quantum double rings (QDRs are studied. Our model can be used to calculate the electronic structures of quantum wells, wires, dots, and the single ring. In calculations, the effects due to the different effective masses of electrons and holes in GaAs and AlxGa1-xAs and the valence band mixing are considered. The energy levels of electrons and holes are calculated for different shapes of QDRs. The calculated results are useful in designing and fabricating the interrelated photoelectric devices. The single electron states presented here are useful for the study of the electron correlations and the effects of magnetic fields in QDRs.

  17. Structural investigations of LiFePO4 electrodes and in situ studies by Fe X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Deb, Aniruddha; Bergmann, Uwe; Cramer, S.P.; Cairns, Elton J.

    2005-01-01

    Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on electrodes containing LiFePO 4 to determine the local atomic and electronic structure and their stability with electrochemical cycling. A versatile electrochemical in situ cell has been constructed for long-term soft and hard X-ray experiments for the structural investigation on battery electrodes during the lithium-insertion/extraction processes. The device is used here for an X-ray absorption spectroscopic study of lithium insertion/extraction in a LiFePO 4 electrode, where the electrode contained about 7.7 mg of LiFePO 4 on a 20 μm thick Al-foil. Fe K-edge X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) have been performed on this electrode to determine the local atomic and electronic structure and their stability with electrochemical cycling. The initial state (LiFePO 4 ) showed iron to be in the Fe 2+ state corresponding to the initial state (0.0 mAh) of the cell, whereas in the delithiated state (FePO 4 ) iron was found to be in the Fe 3+ state corresponding to the final charged state (3 mAh). XANES region of the XAS spectra revealed a high spin configuration for the two states (Fe (II), d 6 and Fe (III), d 5 ). The results confirm that the olivine structure of the LiFePO 4 and FePO 4 is retained by the electrodes in agreement with the XRD observations reported previously. These results confirm that LiFePO 4 cathode material retains good structural short-range order leading to superior cycling capability

  18. Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

    2018-04-11

    In this paper, a vacuum compatible microfluidic device, System for Analysis at the Liquid Vacuum Interface (SALVI), is integrated to hard x-ray absorption spectroscopy (XAS) to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel of 500 μm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra show that the complex in water is Fe(III). The complex is present with octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities and it is a viable approach to enable multifaceted measurements of liquids in the future.

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

    Science.gov (United States)

    Zhan, Fei; Tao, Ye; Zhao, Haifeng

    2017-07-01

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

  20. XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

    Science.gov (United States)

    Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

    2015-03-28

    Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

  1. Local environment of zirconium in nuclear gels studied by XAS

    International Nuclear Information System (INIS)

    Pelegrin, E.; Ildefonse, Ph.; Calas, G.; Ricol, St.; Flank, A.M.

    1997-01-01

    During lixiviation experiments, nuclear gels are formed and heavy metals are retained. In order to understand this retardation mechanisms, we performed an analysis of the local environment of Zr in parent glasses and derived alteration gels both at the Zr-L II,III , and Zr-K edges. Calibration of the method was conducted through the analysis of model compounds with known coordination number (CN): catapleite Na 2 ZrSi 3 O 9 ,2H 2 O (CN=6), baddeleyite ZrO 2 (CN=7) and zircon SiZrO 4 (CN=8). Nuclear glasses (R7T7, and a simplified nuclear glass V 1) and gels obtained at 90 deg C, with leaching times from 7 to 12 months and with solution renewal. were also investigated (GR7T7R and GV1). Zr-L II,III XANES spectra evidenced that zirconium is 6-fold coordinated in R7T7 and V1 nuclear glasses. For GR7T7R and GV1 gels, Zr local environment is significantly changed, and a mixture of CN (6 and 7J has been evidenced. Quantitative structural results were derived from EXAFS analysis at Zr-K edge. In parent glasses, derived Zr-O distance is 2.10±0.01 10 -10 m, and is in the range Zr-O distances for octahedral coordination in model compounds. In both gels studied, Zr-O distances increase significantly up to 2.15 ±0.01 10 -10 m. This distance is close to that known in baddeleyite (2,158 10 -10 m). A better understanding of the Zr retention mechanism has to be made by studying the second neighbors contributions. (authors)

  2. BETA SPECTRA. I. Negatrons spectra

    International Nuclear Information System (INIS)

    Grau Malonda, A.; Garcia-Torano, E.

    1978-01-01

    Using the Fermi theory of beta decay, the beta spectra for 62 negatrons emitters have been computed introducing a correction factor for unique forbidden transitions. These spectra are plotted vs. energy, once normal i sed, and tabulated with the related Fermi functions. The average and median energies are calculated. (Author)

  3. Arsenic speciation in solids using X-ray absorption spectroscopy

    Science.gov (United States)

    Foster, Andrea L.; Kim, Chris S.

    2014-01-01

    Synchrotron-based X-ray absorption spectroscopy (XAS) is an in situ, minimally-destructive, element-specific, molecular-scale structural probe that has been employed to study the chemical forms (species) of arsenic (As) in solid and aqueous phases (including rocks, soils, sediment, synthetic compounds, and numerous types of biota including humans) for more than 20 years. Although several excellent reviews of As geochemistry and As speciation in the environment have been published previously (including recent contributions in this volume), the explosion of As-XAS studies over the past decade (especially studies employing microfocused X-ray beams) warrants this new review of the literature and of data analysis methods.

  4. Simultaneous observations of electromagnetically induced transparency (EIT) and absorption (EIA) in a multi-level V-type system of 87Rb and theoretical simulation of the observed spectra using a multi-mode approach.

    Science.gov (United States)

    Das, Bankim Chandra; Bhattacharyya, Dipankar; Das, Arpita; Chakrabarti, Shrabana; De, Sankar

    2016-12-14

    We report here simultaneous experimental observation of Electromagnetically Induced Transparency (EIT) and Electromagnetically Induced Absorption (EIA) in a multi-level V-type system in D 2 transition of Rb87, i.e., F=2→F ' with a strong pump and a weak probe beam. We studied the probe spectrum by locking the probe beam to the transition F=2→F ' =2 while the pump is scanned from F=2→F ' . EIA is observed for the open transition (F=2→F ' =2) whereas EIT is observed in the closed transition (F=2→F ' =3). Sub natural line-width is observed for the EIA. To simulate the observed spectra theoretically, Liouville equation for the three-level V-type system is solved analytically with a multi-mode approach for the density matrix elements. We assumed both the pump and the probe beams can couple the excited states. A multi-mode approach for the coherence terms facilitates the study of all the frequency contributions due to the pump and the probe fields. Since the terms contain higher harmonics of the pump and the probe frequencies, we expressed them in Fourier transformed forms. To simulate the probe spectrum, we have solved inhomogeneous difference equations for the coherence terms using the Green's function technique and continued fraction theory. The experimental line-widths of the EIT and the EIA are compared with our theoretical model. Our system can be useful in optical switching applications as it can be precisely tuned to render the medium opaque and transparent simultaneously.

  5. Optical Control of Intersubband Absorption in a Multiple Quantum Well-Embedded Semiconductor Microcravity

    Science.gov (United States)

    Liu, Ansheng; Ning, Cun-Zheng

    2000-01-01

    Optical intersubband response of a multiple quantum well (MQW)-embedded microcavity driven by a coherent pump field is studied theoretically. The n-type doped MQW structure with three subbands in the conduction band is sandwiched between a semi-infinite medium and a distributed Bragg reflector (DBR). A strong pump field couples the two upper subbands and a weak field probes the two lower subbands. To describe the optical response of the MQW-embedded microcavity, we adopt a semi-classical nonlocal response theory. Taking into account the pump-probe interaction, we derive the probe-induced current density associated with intersubband transitions from the single-particle density-matrix formalism. By incorporating the current density into the Maxwell equation, we solve the probe local field exactly by means of Green's function technique and the transfer-matrix method. We obtain an exact expression for the probe absorption coefficient of the microcavity. For a GaAs/Al(sub x)Ga(sub 1-x)As MQW structure sandwiched between a GaAs/AlAs DBR and vacuum, we performed numerical calculations of the probe absorption spectra for different parameters such as pump intensity, pump detuning, and cavity length. We find that the probe spectrum is strongly dependent on these parameters. In particular, we find that the combination of the cavity effect and the Autler-Townes effect results in a triplet in the optical spectrum of the MQW system. The optical absorption peak value and its location can be feasibly controlled by varying the pump intensity and detuning.

  6. The Silicon Environment in Silica Polymorphs, Aluminosilicate Crystals and Melts: An In Situ High Temperature XAS Study

    International Nuclear Information System (INIS)

    Cormier, L.; Neuville, D. R.; Roux, J.; Ligny, D. de; Henderson, G. S.; Flank, A.-M.; Lagarde, P.

    2007-01-01

    High temperature X-ray absorption spectroscopy at the Si K-edge has been used to obtain in situ information on SiO2 phase transitions upon heating. Important modifications are observed for the XANES spectra of the high temperature polymorphs, in relation to disordering of the SiO4 tetrahedra beyond the short-range correlations. This paper also presents the XANES spectra of anorthite (CaAl2Si2O8) from room temperature up to the melt (1900 K). This study shows the possibilities for determining the Si environment in crystals and glasses up to the liquid state using in situ XANES measurements

  7. X-ray absorption spectroscopy: EXAFS and XANES - A versatile tool to study the atomic and electronic structure of materials

    International Nuclear Information System (INIS)

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

    1990-01-01

    X-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-ray Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, they will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and sample limitations

  8. X-ray absorption and emission study of amorphous and nanocrystalline GaN films containing buried N2

    International Nuclear Information System (INIS)

    Ruck, B.J.; Koo, A.; Budde, F.; Granville, S.; Trodahl, H.J.

    2004-01-01

    Full text: It has been predicted that amorphous gallium nitride (a-GaN) may possess a well-defined wide band gap, and is thus a potential substitute for the more expensive crystalline form used in short wavelength optoelectronic devices. Experimental investigations of disordered GaN have lent support to this prediction, but the picture is complicated because the properties of the amorphous state are not unique, and instead depend on the exact nature of the disordered structure. We have pioneered a novel ion-assisted growth technique that produces GaN films with a microstructure that ranges from nanocrystalline, with crystallite size of order 3 nm, to fully amorphous, depending on the exact growth conditions. This presentation will give an overview of our research into the properties of disordered GaN, including characterization of the physical structure of the films and their electronic energy levels, and also their photoconductive response. In particular I will focus on synchrotron radiation studies of samples with a range of different microstructures. X-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) provide particularly powerful tools for examining a sample's empty and filled electronic energy levels, respectively. The details of the absorption and emission processes make it possible to obtain atom-specific information and to investigate the symmetry of the electronic levels. An example of the information obtained is shown. The thin solid curve shows XAS data, which is a measure of the nitrogen /7-projected density of unfilled electronic states in this nanocrystalline GaN sample. The thick solid curve shows XES data from the same sample, which provides complementary information about the occupied valence band states. Although the spectral features are broader in fully amorphous films than in nanocrystalline samples, a well-defined band gap exists in both cases with magnitude similar to that of crystalline GaN. There are additional feature

  9. A superconducting tunneling junction (STJ) detector for soft X-ray absorption spectroscopy at 50 mK

    International Nuclear Information System (INIS)

    Baev, Ivan; Ruescher, Jan-Hendrik; Martins, Michael; Viefhaus, Jens; Wurth, Wilfried

    2016-01-01

    Soft X-ray absorption spectroscopy (XAS) is an important technique at synchrotrons nowadays that allows to investigate electronic and magnetic properties in an element specific way. The investigation of non-conductive, soft organic or buried materials can't be carried out in total electron yield. In these cases an efficient fluorescence detector is needed to perform XAS measurements in partial fluorescence yield (PFY). The STJ detector is capable of count rates as high as 10 kcps per 100 μm"2 pixel size with an energy resolution of approximately 50 eV for 1.5 keV photons. The STJ is furthermore integrated into a 50 mK cryostat for XAS measurements at the P04 beamline at Petra III, DESY. We will present first measurements on a model system.

  10. Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering

    Science.gov (United States)

    Yang, Wanli; Devereaux, Thomas P.

    2018-06-01

    Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

  11. Optical absorption of irradiated carbohydrates

    International Nuclear Information System (INIS)

    Supe, A.A.; Tiliks, Yu.E.

    1994-01-01

    The optical absorption spectra of γ-irradiated carbohydrates (glucose, lactose, sucrose, maltose, and starch) and their aqueous solutions were studied. The comparison of the data obtained with the determination of the concentrations of molecular and radical products of radiolysis allows the absorption bands with maxima at 250 and 310 nm to be assigned to the radicals trapped in the irradiated carbohydrates

  12. Coelectrodeposition of Ternary Mn-Oxide/Polypyrrole Composites for ORR Electrocatalysts: A Study Based on Micro-X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping

    Directory of Open Access Journals (Sweden)

    Benedetto Bozzini

    2015-08-01

    Full Text Available Low energy X-ray fluorescence (XRF and soft X-ray absorption (XAS microspectroscopies at high space-resolution are employed for the investigation of the coelectrodeposition of composites consisting of a polypyrrole(PPy-matrix and Mn-based ternary dispersoids, that have been proposed as promising electrocatalysts for oxygen-reduction electrodes. Specifically, we studied Mn–Co–Cu/PP, Mn–Co–Mg/PPy and Mn–Ni–Mg/PPy co-electrodeposits. The Mn–Co–Cu system features the best ORR electrocatalytic activity in terms of electron transfer number, onset potential, half-wave potential and current density. XRF maps and micro-XAS spectra yield compositional and chemical state distributions, contributing unique molecular-level information on the pulse-plating processes. Mn, Ni, Co and Mg exhibit a bimodal distribution consisting of mesoscopic aggregates of micrometric globuli, separated by polymer-rich ridges. Within this common qualitative scenario, the individual systems exhibit quantitatively different chemical distribution patterns, resulting from specific electrokinetic and electrosorption properties of the single components. The electrodeposits consist of Mn3+,4+-oxide particles, accompanied by combinations of Co0/Co2+, Ni0/Ni2+ and Cu0,+/Cu2+ resulting from the alternance of cathodic and anodic pulses. The formation of highly electroactive Mn3+,4+ in the as-fabricated material is a specific feature of the ternary systems, deriving from synergistic stabilisation brought about by two types of bivalent dopants as well as by galvanic contact to elemental metal; this result represents a considerable improvement in material quality with respect to previously studied Mn/PPy and Mn-based/PPy binaries.

  13. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory.

    Science.gov (United States)

    Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; Scheinost, Andreas; Moisy, Philippe; Petit, Sébastien; Shuh, David K; Tyliszczak, Tolek; Den Auwer, Christophe

    2016-01-28

    The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide better resolution than actinide L3-edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L2,3-edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K4Fe(II)(CN)6, thorium hexacyanoferrate Th(IV)Fe(II)(CN)6, and neodymium hexacyanoferrate KNd(III)Fe(II)(CN)6. The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe(II)(CN)6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K4Fe(II)(CN)6), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.

  14. UV and infrared absorption spectra, atmospheric lifetimes, and ozone depletion and global warming potentials for CCl2FCCl2F (CFC-112, CCl3CClF2 (CFC-112a, CCl3CF3 (CFC-113a, and CCl2FCF3 (CFC-114a

    Directory of Open Access Journals (Sweden)

    M. E. Davis

    2016-07-01

    Full Text Available The potential impact of CCl2FCF3 (CFC-114a and the recently observed CCl2FCCl2F (CFC-112, CCl3CClF2 (CFC-112a, and CCl3CF3 (CFC-113a chlorofluorocarbons (CFCs on stratospheric ozone and climate is presently not well characterized. In this study, the UV absorption spectra of these CFCs were measured between 192.5 and 235 nm over the temperature range 207–323 K. Precise parameterizations of the UV absorption spectra are presented. A 2-D atmospheric model was used to evaluate the CFC atmospheric loss processes, lifetimes, ozone depletion potentials (ODPs, and the associated uncertainty ranges in these metrics due to the kinetic and photochemical uncertainty. The CFCs are primarily removed in the stratosphere by short-wavelength UV photolysis with calculated global annually averaged steady-state lifetimes (years of 63.6 (61.9–64.7, 51.5 (50.0–52.6, 55.4 (54.3–56.3, and 105.3 (102.9–107.4 for CFC-112, CFC-112a, CFC-113a, and CFC-114a, respectively. The range of lifetimes given in parentheses is due to the 2σ uncertainty in the UV absorption spectra and O(1D rate coefficients included in the model calculations. The 2-D model was also used to calculate the CFC ozone depletion potentials (ODPs with values of 0.98, 0.86, 0.73, and 0.72 obtained for CFC-112, CFC-112a, CFC-113a, and CFC-114a, respectively. Using the infrared absorption spectra and lifetimes determined in this work, the CFC global warming potentials (GWPs were estimated to be 4260 (CFC-112, 3330 (CFC-112a, 3650 (CFC-113a, and 6510 (CFC-114a for the 100-year time horizon.

  15. Raman spectra of lithium compounds

    Science.gov (United States)

    Gorelik, V. S.; Bi, Dongxue; Voinov, Y. P.; Vodchits, A. I.; Gorshunov, B. P.; Yurasov, N. I.; Yurasova, I. I.

    2017-11-01

    The paper is devoted to the results of investigating the spontaneous Raman scattering spectra in the lithium compounds crystals in a wide spectral range by the fibre-optic spectroscopy method. We also present the stimulated Raman scattering spectra in the lithium hydroxide and lithium deuteride crystals obtained with the use of powerful laser source. The symmetry properties of the lithium hydroxide, lithium hydroxide monohydrate and lithium deuteride crystals optical modes were analyzed by means of the irreducible representations of the point symmetry groups. We have established the selection rules in the Raman and infrared absorption spectra of LiOH, LiOH·H2O and LiD crystals.

  16. The relationship between Al and Si in biogenic silica as determined by PIXE and XAS

    International Nuclear Information System (INIS)

    Beck, L.; Gehlen, M.; Flank, A.-M.; Bennekom, A.J. van; Beusekom, J.E.E. van

    2002-01-01

    Biogenic silica, one of the major constituents of marine sediments, is a potentially powerful paleoceanographic tool, revealing information on past productivity. Interpreting the sedimentary records of the biogenic silica requires, however, an understanding of its preservation. Dissolution of biogenic silica is controlled by the presence of trace elements such as Al. The work in this paper focuses on the association of Al and Si in biogenic silica. The composition and the atomic structure of cultured and natural diatoms were determined by using PIXE and XAS techniques. This study provides the first evidence for a structural association of Al and Si in biogenic silica

  17. Spectroscopic verification of zinc absorption and distribution in the desert plant Prosopis juliflora-velutina (velvet mesquite) treated with ZnO nanoparticles.

    Science.gov (United States)

    Hernandez-Viezcas, J A; Castillo-Michel, H; Servin, A D; Peralta-Videa, J R; Gardea-Torresdey, J L

    2011-06-01

    The impact of metal nanoparticles (NPs) on biological systems, especially plants, is still not well understood. The aim of this research was to determine the effects of zinc oxide (ZnO) NPs in velvet mesquite (Prosopis juliflora-velutina). Mesquite seedlings were grown for 15 days in hydroponics with ZnO NPs (10 nm) at concentrations varying from 500 to 4000 mg L(-1). Zinc concentrations in roots, stems and leaves were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Plant stress was examined by the specific activity of catalase (CAT) and ascorbate peroxidase (APOX); while the biotransformation of ZnO NPs and Zn distribution in tissues was determined by X-ray absorption spectroscopy (XAS) and micro X-ray fluorescence (μXRF), respectively. ICP-OES results showed that Zn concentrations in tissues (2102 ± 87, 1135 ± 56, and 628 ± 130 mg kg(-1) d wt in roots, stems, and leaves, respectively) were found at 2000 mg ZnO NPs L(-1). Stress tests showed that ZnO NPs increased CAT in roots, stems, and leaves, while APOX increased only in stems and leaves. XANES spectra demonstrated that ZnO NPs were not present in mesquite tissues, while Zn was found as Zn(II), resembling the spectra of Zn(NO(3))(2). The μXRF analysis confirmed the presence of Zn in the vascular system of roots and leaves in ZnO NP treated plants.

  18. Lattice vibration spectra. 16

    International Nuclear Information System (INIS)

    Lutz, H.D.; Willich, P.

    1977-01-01

    The FIR absorption spectra of pyrite type compounds RuS 2 , RuSsub(2-x)Sesub(x), RuSe 2 , RuTe 2 , OsS 2 , OsSe 2 , and PtP 2 as well as loellingite type phosphides FeP 2 , RuP 2 , and OsP 2 are reported. For RuS 2 , RuSe 2 , RuTe 2 , OsS 2 , and PtP 2 all of the five infrared allowed modes (k = 0) are observed. As a first result of a numerical normal coordinate treatment vibration forms of pyrite structure are communicated. The spectra show that lattice forces of corresponding sulfides, tellurides, and phosphides are about the same strength, but increase strongly by substitution of iron by ruthenium and especially of ruthenium by osmium. The lattice constants of the RuSsub(2-x)Sesub(x) solid solution obey Vegard's rule. (author)

  19. Quasar Absorption Studies

    Science.gov (United States)

    Mushotzky, Richard (Technical Monitor); Elvis, Martin

    2004-01-01

    The aim of the proposal is to investigate the absorption properties of a sample of inter-mediate redshift quasars. The main goals of the project are: Measure the redshift and the column density of the X-ray absorbers; test the correlation between absorption and redshift suggested by ROSAT and ASCA data; constrain the absorber ionization status and metallicity; constrain the absorber dust content and composition through the comparison between the amount of X-ray absorption and optical dust extinction. Unanticipated low energy cut-offs where discovered in ROSAT spectra of quasars and confirmed by ASCA, BeppoSAX and Chandra. In most cases it was not possible to constrain adequately the redshift of the absorber from the X-ray data alone. Two possibilities remain open: a) absorption at the quasar redshift; and b) intervening absorption. The evidences in favour of intrinsic absorption are all indirect. Sensitive XMM observations can discriminate between these different scenarios. If the absorption is at the quasar redshift we can study whether the quasar environment evolves with the Cosmic time.

  20. A structural study of ceramic oxides by X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Akhtar, M.J.

    1995-01-01

    A detailed structural study of ceramic oxides is presented by employing X-ray Absorption Spectroscopy (XAS). In the present work X-ray Absorption Near Edge Structure (XANES) is used for the investigation of valence state of metal cations; whereas, Extended X-ray Absorption Fine Structure EXAFS) is employed for the determination for bond lengths, coordination numbers and nature of the elements present in the near neighbour shells surrounding the absorbing atom. These results show that local environment of dopant and host cations are different; and this variation in local structure depends on the nature and concentration of the dopant ions. (author)

  1. Role of Bi promotion and solvent in platinum-catalyzed alcohol oxidation probed by in situ X-ray absorption and ATR-IR spectroscopy

    DEFF Research Database (Denmark)

    Mondelli, C.; Grunwaldt, Jan-Dierk; Ferri, D.

    2010-01-01

    the catalysts under working conditions using in situ X-ray absorption spectroscopy (XAS) and attenuated total reflection infrared spectroscopy (ATR-IR), aiming at uncovering the roles of the metal promoter and the reaction medium. XAS confirms that Bi is oxidized more easily than Pt, maintaining the catalytic...... surfaces than on step or kink sites. Side products, CO and benzoate species, appearing during the reaction reveal that the geometric suppression of undesired reactions does not occur to the same extent on Pt-based catalysts as on Pd, suggesting that decarbonylation of the produced aldehyde on Pt may occur...

  2. X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

  3. From structure to spectra. Tight-binding theory of InGaAs quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Goldmann, Elias

    2014-07-23

    Self-assembled semiconductor quantum dots have raised considerable interest in the last decades due to a multitude of possible applications ranging from carrier storage to light emitters, lasers and future quantum communication devices. Quantum dots offer unique electronic and photonic properties due to the three-dimensional confinement of charge carriers and the coupling to a quasi-continuum of wetting layer and barrier states. In this work we investigate the electronic structure of In{sub x}Ga{sub 1-x}As quantum dots embedded in GaAs, considering realistic quantum dot geometries and Indium concentrations. We utilize a next-neighbour sp{sup 3}s{sup *} tight-binding model for the calculation of electronic single-particle energies and wave functions bound in the nanostructure and account for strain arising from lattice mismatch of the constituent materials atomistically. With the calculated single-particle wave functions we derive Coulomb matrix elements and include them into a configuration interaction treatment, yielding many-particle states and energies of the interacting many-carrier system. Also from the tight-binding single-particle wave functions we derive dipole transition strengths to obtain optical quantum dot emission and absorption spectra with Fermi's golden rule. Excitonic fine-structure splittings are obtained, which play an important role for future quantum cryptography and quantum communication devices for entanglement swapping or quantum repeating. For light emission suited for long-range quantum-crypted fiber communication InAs quantum dots are embedded in an In{sub x}Ga{sub 1-x}As strain-reducing layer, shifting the emission wavelength into telecom low-absorption windows. We investigate the influence of the strain-reducing layer Indium concentration on the excitonic finestructure splitting. The fine-structure splitting is found to saturate and, in some cases, even reduce with strain-reducing layer Indium concentration, a result being

  4. Characterization of heterogeneous SiO2 materials by scanning electron microscope and micro fluorescence XAS techniques

    International Nuclear Information System (INIS)

    Khouchaf, L.; Boinski, F.; Tuilier, M.H.; Flank, A.M.

    2006-01-01

    Micro X-ray absorption near edge structure XANES and micro fluorescence experiments have been carried out using X-ray microbeam from synchrotron radiation source with high brightness to investigate the local structural evolutions of heterogeneous and natural SiO 2 submitted to alkali-silica reaction ASR process. Compared to elemental maps obtained by Environmental Scanning Electron Microscope ESEM, micro fluorescence X maps showed the diffusion of potassium cations inside the grains with higher accuracy. Si K-edge spectra show the disorder induced by the dissolution of the grain from the outside to the inside. Potassium K-edge spectra do not show significant changes around K cations. The breaking of Si-O-Si bonds and the disorder of the (SiO 4 ) n network may be affected to potassium cations

  5. Characterization of heterogeneous SiO{sub 2} materials by scanning electron microscope and micro fluorescence XAS techniques

    Energy Technology Data Exchange (ETDEWEB)

    Khouchaf, L. [Centre de Recherche de l' Ecole des Mines deDouai, 941, rue Charles Bourseul, BP. 10838, 59508 Douai (France)]. E-mail: khouchaf@ensm-douai.fr; Boinski, F. [Centre de Recherche de l' Ecole des Mines deDouai, 941, rue Charles Bourseul, BP. 10838, 59508 Douai (France); Tuilier, M.H. [GMP Equipe de recherche: MMPF, Universite de Haute-Alsace, 61 rue Albert Camus, F-68093, Mulhouse Cedex (France); Flank, A.M. [SOLEIL and Swiss Light Source SLS CH-5232 Villigen PSI (Switzerland)

    2006-11-15

    Micro X-ray absorption near edge structure XANES and micro fluorescence experiments have been carried out using X-ray microbeam from synchrotron radiation source with high brightness to investigate the local structural evolutions of heterogeneous and natural SiO{sub 2} submitted to alkali-silica reaction ASR process. Compared to elemental maps obtained by Environmental Scanning Electron Microscope ESEM, micro fluorescence X maps showed the diffusion of potassium cations inside the grains with higher accuracy. Si K-edge spectra show the disorder induced by the dissolution of the grain from the outside to the inside. Potassium K-edge spectra do not show significant changes around K cations. The breaking of Si-O-Si bonds and the disorder of the (SiO{sub 4}) {sub n} network may be affected to potassium cations.

  6. In situ XAS study of the Mn(III)(salen)Br catalyzed synthesis of cyclic organic carbonates from epoxides and CO2

    DEFF Research Database (Denmark)

    Jutz, Fabian; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2009-01-01

    In situ X-ray absorption spectroscopy at the Mn K- and Br K-edge was employed to study the cycloaddition of carbon dioxide to propylene oxide and styrene oxide, catalyzed by Mn(III) salen bromide complexes. Three homogeneous complexes with varying salen ligand structure and one complex immobilized...... coordination of the bromine neighbors to the Mn central atom was also evidenced by EXAFS spectra, e.g. loss of Br backscattering in the Mn K-EXAFS spectra and the Mn-backscattering in the Br K-edge spectra. In the catalytic studies it was observed that propylene oxide usually reacted much faster than styrene...

  7. Subgap absorption in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Sinclair, M.; Seager, C.H. (Sandia National Labs., Albuquerque, NM (USA)); McBranch, D.; Heeger, A.J. (California Univ., Santa Barbara, CA (USA)); Baker, G.L. (Bell Communications Research, Inc., Red Bank, NJ (USA))

    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. 11 refs., 4 figs.

  8. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Patridge, Christopher J. [NRC/NRL Cooperative Research Associate, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Love, Corey T., E-mail: corey.love@nrl.navy.mil [Chemistry Division, Code 6113, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Swider-Lyons, Karen E. [Chemistry Division, Code 6113, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Twigg, Mark E. [Electronics Science and Technology Division, Code 6812, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Ramaker, David E. [Chemistry Division, Code 6189, U.S. Naval Research laboratory, Washington, DC 20375 (United States)

    2013-07-15

    The local structure of nanoscale (∼10–40 nm) LiCoO{sub 2} is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO{sub 2} nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO{sub 2} metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO{sub 2} as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO{sub 2}. - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO{sub 2} to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO{sub 2}. • Surface structural changes are emphasized using nanoscale-LiCoO{sub 2} and difference spectra. • Full multiple

  9. In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

    International Nuclear Information System (INIS)

    Patridge, Christopher J.; Love, Corey T.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

    2013-01-01

    The local structure of nanoscale (∼10–40 nm) LiCoO 2 is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO 2 nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO 2 metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO 2 as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO 2 . - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO 2 to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO 2 . • Surface structural changes are emphasized using nanoscale-LiCoO 2 and difference spectra. • Full multiple scattering calculations are used to

  10. Calcium absorption

    International Nuclear Information System (INIS)

    Carlmark, B.; Reizenstein, P.; Dudley, R.A.

    1976-01-01

    The methods most commonly used to measure the absorption and retention of orally administered calcium are reviewed. Nearly all make use of calcium radioisotopes. The magnitude of calcium absorption and retention depends upon the chemical form and amount of calcium administered, and the clinical and nutritional status of the subject; these influences are briefly surveyed. (author)

  11. Absorption studies

    International Nuclear Information System (INIS)

    Ganatra, R.D.

    1992-01-01

    Absorption studies were once quite popular but hardly anyone does them these days. It is easier to estimate the blood level of the nutrient directly by radioimmunoassay (RIA). However, the information obtained by estimating the blood levels of the nutrients is not the same that can be obtained from the absorption studies. Absorption studies are primarily done to find out whether some of the essential nutrients are absorbed from the gut or not and if they are absorbed, to determine how much is being absorbed. In the advanced countries, these tests were mostly done to detect pernicious anaemia where vitamin B 12 is not absorbed because of the lack of the intrinsic factor in the stomach. In the tropical countries, ''malabsorption syndrome'' is quire common. In this condition, several nutrients like fat, folic acid and vitamin B 12 are not absorbed. It is possible to study absorption of these nutrients by radioisotopic absorption studies

  12. Spectral interferences in atomic absorption spectrometry, (5)

    International Nuclear Information System (INIS)

    Daidoji, Hidehiro

    1979-01-01

    Spectral interferences were observed in trace element analysis of concentrated solutions by atomic absorption spectrometry. Molecular absorption and emission spectra for strontium chloride and nitrate, barium chloride and nitrate containing 12 mg/ml of metal ion in airacetylene flame were measured in the wavelength range from 200 to 700 nm. The absorption and emission spectra of SrO were centered near 364.6 nm. The absorption spectra of SrOH around 606.0, 671.0 and 682.0 nm were very strong. And, emission spectrum of BaOH in the wavelength range from 480 to 550 nm was stronger. But, the absorption of this band spectrum was very weak. In the wavelength range from 200 to 400 nm, some unknown bands of absorption were observed for strontium and barium. Absorption spectra of SrCl and BaCl were observed in the argon-hydrogen flame. Also, in the carbon tube atomizer, the absorption spectra of SrCl and BaCl were detected clearly in the wavelength range from 185 to 400 nm. (author)

  13. Crystal-field analysis for RE3+ ions in laser materials: II. Absorption spectra and energy levels calculations for Nd3+ ions doped into SrLaGa3O7 and BaLaGa3O7 crystals and Tm3+ ions in SrGdGa3O7

    International Nuclear Information System (INIS)

    Karbowiak, M.; Gnutek, P.; Rudowicz, C.; Ryba-Romanowski, W.

    2011-01-01

    Graphical abstract: In this paper we report a detailed analysis of spectroscopic data obtained from low temperature absorption spectra, which enabled assignment of energy levels, and subsequently their analysis in terms of the free-ion and crystal field (CF) parameters. Highlights: → Polarized absorption spectra measured for Nd 3+ and Tm 3+ ions in ABC 3 O 7 crystals. → Energy levels analyzed in terms of the free-ion and crystal-field (CF) parameters. → The combined ADS/SPM procedure have been successfully applied. → The B-bar k parameters and the power law exponents t k of SPM model are determined. → The energies of levels are important for evaluation of the emission cross-section. - Abstract: Low temperature polarized absorption spectra are analyzed to achieve assignments of energy levels for Nd 3+ and Tm 3+ ions at monoclinic C s site symmetry in ABC 3 O 7 crystals. Based on the concept of average optical center, the experimental energy levels for single crystals of SrLaGa 3 O 7 :Nd 3+ (SLG:Nd), BaLaGa 3 O 7 :Nd 3+ (BLG:Nd), and SrGdGa 3 O 7 :Tm 3+ (SGG:Tm) were analyzed in terms of the free-ion parameters and the crystal field (CF) ones, B kq . Assignments of the energy levels resolved in the spectra were done in stages applying the ascent/descent in symmetry method in CF analysis. The actual monoclinic C s site symmetry at the metal centers in ABC 3 O 7 crystals and the approximated orthorhombic C 2v and tetragonal C 4v symmetry were considered. The starting values of B kq 's for SLG:Nd and BLG:Nd crystals were obtained from superposition model (SPM) analysis. The final fitted crystal field parameters show high compatibility with the existing data for structurally similar ion-host systems. The obtained values of the intrinsic parameters provide basis for SPM analysis of CF parameters for rare earth ions in other similar systems, especially those exhibiting low-symmetry sites. The SPM parameters derived for SLG:Nd are used for simulation and

  14. I20; the Versatile X-ray Absorption spectroscopy beamline at Diamond Light Source

    International Nuclear Information System (INIS)

    Diaz-Moreno, S; Hayama, S; Amboage, M; Freeman, A; Sutter, J; Duller, G

    2009-01-01

    The Versatile Spectroscopy beamline at Diamond Light Source, I20, is currently under construction and aims to begin operation in late 2009 and early 2010. The beamline aims to cover applications from physics, chemistry and biology through materials, environmental and geological science. Three very distinctive modes of operation will be offered at the beamline: scanning X-ray Absorption spectroscopy (XAS), XAS in dispersive mode, and X-ray emission spectroscopy (XES). To achieve this, the beamline has been designed around two independent experimental end-stations operating from a pair of canted wigglers located in a 5m diamond straight section. One branch of the beamline will deliver monochromatic x-ray radiation of high spectral purity to one of the experimental hutches, whilst the other branch will constitute an energy dispersive spectrometer. The novel design of the beamline allows both branches to operate simultaneously.

  15. Folate absorption

    International Nuclear Information System (INIS)

    Baker, S.J.

    1976-01-01

    Folate is the generic term given to numerous compounds of pteroic acid with glutamic acid. Knowledge of absorption is limited because of the complexities introduced by the variety of compounds and because of the inadequacy of investigational methods. Two assay methods are in use, namely microbiological and radioactive. Techniques used to study absorption include measurement of urinary excretion, serum concentration, faecal excretion, intestinal perfusion, and haematological response. It is probably necessary to test absorption of both pteroylmonoglutamic acid and one or more polyglutamates, and such tests would be facilitated by availability of synthesized compounds labelled with radioactive tracers at specifically selected sites. (author)

  16. Biological Action Spectra (invited paper)

    International Nuclear Information System (INIS)

    Gruijl, F.R. de

    2000-01-01

    Ultraviolet (UV) radiation induces a wide variety of biological responses: ranging in humans from well-known short-term effects like sunburn to long-term effects like skin cancer. The wavelength dependencies ('action spectra') of the responses can differ significantly, depending on the UV-targeted molecules (their absorption spectra), their localisation (transmission to the target depth) and the photochemical reactions involved (e.g. quantum yields, competing reaction). An action spectrum (e.g. of sunburn) is usually determined in a wavelength by wavelength analysis of the response. This is not always possible (e.g. in case of skin cancer), and an action spectrum may then be extracted mathematically from differences in responses to broadband UV sources of various spectral compositions (yielding 'biological spectral weights'). However, relative spectral weights may shift with exposure levels and contributions from different wavelengths may not always add up. Under these circumstances conventional analyses will yield different action spectra for different experimental conditions. (author)

  17. Subgap Absorption in Conjugated Polymers

    Science.gov (United States)

    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 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.

  18. Acoustic phonon dephasing in shallow GaAs/Ga 1- xAl xAs single quantum wells

    Science.gov (United States)

    Cassabois, G.; Meccherini, S.; Roussignol, Ph.; Bogani, F.; Gurioli, M.; Colocci, M.; Planel, R.; Thierry-Mieg, V.

    1998-07-01

    The intermediate dimensionality regime is studied on a set of shallow GaAs/Ga 1- xAl xAs single quantum wells. Such heterostructures exhibit 2D strong excitonic electroabsorption together with near 3D fast transport properties. We report dephasing time measurements ( T2) of the heavy-hole exciton and we show that the acoustic phonon contribution decreases with x to a value in good agreement with theoretical predictions for GaAs bulk.

  19. XAS Investigation of bio-relevant cobalt complexes in aqueous media

    International Nuclear Information System (INIS)

    Bresson, C.; Lamouroux, C.; Esnouf, S.; Solari, P.L.; Den Auwer, C.

    2006-01-01

    Cobalt is an essential element of biological cycles involved in numerous metallo-biomolecules, but it becomes a toxic element at high concentration or a radio-toxic element because of its use in the nuclear industry. 'Molecular speciation' in biological media is an essential prerequisite to evaluate its chemical behaviour as well as its toxic or beneficial effects. In this scheme, we have focused on the coordination properties of the thiol-containing amino acid cysteine (Cys) and the pseudo-peptide N-(2-mercapto-propionyl) glycine (MPG) towards the Co 2+ cation in aqueous media. XAS at the Co K edge and traditional spectroscopic techniques have been coupled in order to structurally characterize the cobalt coordination sphere. Oxidation states and geometries of the bis- and tris-cysteinato Co(III) complexes are in agreement with the literature data. In addition, bond lengths between the metallic centre and the donor atoms have been determined. The structure of a new dimeric N-(2-mercapto-propionyl) glycinato Co(II) complex in solution is also reported. The coordination of MPG to Co(II) through the thiolate and carboxylate functions is ascertained. This work provides fundamental structural information about bio-relevant complexes of cobalt, which will contribute to our understanding of the chemical behaviour and the biological role of this radionuclide. (authors)

  20. Optical absorption in dendrimers

    International Nuclear Information System (INIS)

    Supritz, C.; Engelmann, A.; Reineker, P.

    2004-01-01

    Dendrimers are highly branched molecules, which are expected to be useful, for example, as efficient artificial light harvesting systems in nano-technological applications. There are two different classes of dendrimers: compact dendrimers with constant distance between neighboring branching points throughout the macromolecule and extended dendrimers, where this distance increases from the system periphery to the center. We investigate the linear absorption spectra of these dendrimer types using the Frenkel exciton concept. The electron-phonon interaction is taken into account by introducing a heat bath that interacts with the exciton in a stochastic manner

  1. A transient absorption study of allophycocyanin

    Indian Academy of Sciences (India)

    Transient dynamics of allophycocyanin trimers and monomers are observed by using the pump-probe, transient absorption technique. The origin of spectral components of the transient absorption spectra is discussed in terms of both kinetics and spectroscopy. We find that the energy gap between the ground and excited ...

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

    Science.gov (United States)

    Itoh, Takanori; Imai, Hideto

    2018-03-01

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

  3. Photoacoustic spectra of rare earth pentaphosphates

    International Nuclear Information System (INIS)

    Strek, W.; Lukowiak, E.; Marchewka, M.; Ratajczak, H.

    1987-01-01

    The photoacoustic (PA) spectra of raee earth pentaphosphates of the general formula REP 5 O 14 , where RE = Pr,Nd,Ho,Er,Tm, are reported. The photoacoustic bands were identified and compared with the absorption spectra. For quantitative analysis of PA bands of lanthanide (III) ions, the intensity ratio vector is introduced characterizing the intensity distribution of f-f transitions. It was found that the relative intensities of photoacoustic bands are comparable with the intensities of absorption bands. It is concluded that the nonradiative relaxation mechanism leading to the PA signal is independent of the manifold-to-manifold J-J' radiationless transitions

  4. Crystal structure and optical absorption spectra of Ga0.5Fe0.5InS3 and Ga0.5Fe0.25In1.25S3 crystals

    International Nuclear Information System (INIS)

    Gusejnov, G.G.; Musaeva, N.N.; Kyazumov, M.G.; Asadova, I.B.; Aliev, O.M.

    2003-01-01

    Single crystals of Ga 0.5 Fe 0.5 InS 3 are grown by the method of chemical gas-transport reactions and those of Ga 0.5 Fe 0.25 In 1.25 S 3 - by Bridgman method. X-ray diffraction studies reveal that they crystallize in trigonal and rhombohedral systems with lattice parameters of a = 3.796 x 2 A, c = 12.210 A, P3m1; a = 3.786 x 2 A, c = 36.606 A, R3m, respectively. An optical absorption edge in a wide range of photon energy and an energy gap width are determined: E g = 1.885 eV for Ga 0.5 Fe 0.5 InS 3 and E g 1.843 eV for Ga 0.5 Fe 0.25 In 1.25 S 3 [ru

  5. Characterization of metallic nanoparticles by high-resolution X-ray absorption and X-ray emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kuehn, Timna-Josua

    2012-03-15

    In almost all areas of technology, metallic nanoparticles are of interest due to their special thermal, electronic, magnetic and optical properties. Their special properties are mainly due to their small size which implies the relevance of quantum effects as well as the significance of the surface: For 2 nm nanoparticles, the surface-to-volume ratio is already 1:1. However, the identification of surface-to-volume interactions - that are responsible for the new properties - is a difficult task due to the small size that inhibits a lot of 'standard' techniques to be applicable. Here X-ray absorption/emission spectroscopy (XAS/XES) is a favorable tool for the characterization of nanoparticles, independent on size, degree of crystallinity and shape/condition of the surface. Using XAS, a tempered nanosized Co{sub 3}Pt/C catalyst have been investigated. Its outstanding oxygen-reduction reaction (ORR) properties in a fuel cell could be related to a lowered Pt 5d-band center connected to a tightened Pt-Pt bonding distance, leading to a weakening of the oxygen adsorption strength so that the ORR may proceed faster. One drawback remains, however, as the properties found by (standard) XAS are summed up for different chemical environments of the chosen element. Thus, no distinction can be made between, e.g., the pure metal in a nanoparticles' interior and the ligated metal in the outer shells or surface. Here, high-resolution fluorescence-detected XAS (HRFD-XAS) provides additional opportunities as, due to its chemical sensitivity, it leads to site-selective XAS. For a system of 6 nm sized Co nanoparticles, build up of a metallic core surrounded by a protecting shell, that resulted from the 'smooth oxidation' process, this technique of site-selective XAS was proven to be applicable. For the first time, the interior and outer shell of a metallic nanoparticle could be characterized separately. In particular, the Co-hcp phase could be determined for the

  6. Narrative absorption

    DEFF Research Database (Denmark)

    Narrative Absorption brings together research from the social sciences and Humanities to solve a number of mysteries: Most of us will have had those moments, of being totally absorbed in a book, a movie, or computer game. Typically we do not have any idea about how we ended up in such a state. No...

  7. Different mathematical processing of absorption, ratio and derivative spectra for quantification of mixtures containing minor component: An application to the analysis of the recently co-formulated antidiabetic drugs; canagliflozin and metformin

    Science.gov (United States)

    Lotfy, Hayam M.; Mohamed, Dalia; Elshahed, Mona S.

    2018-01-01

    In the presented work several spectrophotometric methods were performed for the quantification of canagliflozin (CGZ) and metformin hydrochloride (MTF) simultaneously in their binary mixture. Two of these methods; response correlation (RC) and advanced balance point-spectrum subtraction (ABP-SS) were developed and introduced for the first time in this work, where the latter method (ABP-SS) was performed on both the zero order and the first derivative spectra of the drugs. Besides, two recently established methods; advanced amplitude modulation (AAM) and advanced absorbance subtraction (AAS) were also accomplished. All the proposed methods were validated in accordance to the ICH guidelines, where all methods were proved to be accurate and precise. Additionally, the linearity range, limit of detection and limit of quantification were determined and the selectivity was examined through the analysis of laboratory prepared mixtures and the combined dosage form of the drugs. The proposed methods were capable of determining the two drugs in the ratio present in the pharmaceutical formulation CGZ:MTF (1:17) without the requirement of any preliminary separation, further dilution or standard spiking. The results obtained by the proposed methods were in compliance with the reported chromatographic method when compared statistically, proving the absence of any significant difference in accuracy and precision between the proposed and reported methods.

  8. A flexible gas flow reaction cell for in situ x-ray absorption spectroscopy studies

    Energy Technology Data Exchange (ETDEWEB)

    Kroner, Anna B., E-mail: anna.kroner@diamond.ac.uk; Gilbert, Martin; Duller, Graham; Cahill, Leo; Leicester, Peter; Woolliscroft, Richard; Shotton, Elizabeth J. [Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Chilton, Oxfordshire, OX110DE (United Kingdom); Mohammed, Khaled M. H. [UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX110FA (United Kingdom); School of Chemistry, University of Southampton, Southampton, SO17 1BJ (United Kingdom)

    2016-07-27

    A capillary-based sample environment with hot air blower and integrated gas system was developed at Diamond to conduct X-ray absorption spectroscopy (XAS) studies of materials under time-resolved, in situ conditions. The use of a hot air blower, operating in the temperature range of 298-1173 K, allows introduction of other techniques e.g. X-ray diffraction (XRD), Raman spectroscopy for combined techniques studies. The flexibility to use either quartz or Kapton capillaries allows users to perform XAS measurement at energies as low as 5600 eV. To demonstrate performance, time-resolved, in situ XAS results of Rh catalysts during the process of activation (Rh K-edge, Ce L{sub 3}-edge and Cr K-edge) and the study of mixed oxide membrane (La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ}) under various partial oxygen pressure conditions are described.

  9. Relationship between ferroelectric properties and local structure of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} ceramic materials studied by X-ray absorption and Raman spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Mesquita, Alexandre, E-mail: mesquita@rc.unesp.br [Instituto de Geociências e Ciências Exatas, UNESP – Univ Estadual Paulista, Departamento de Física, Av. 24-a, 1515, Rio Claro, SP 13506-900 (Brazil); Institut de Chimie et des Materiaux Paris Est, CNRS and Université Paris Est Créteil, 2 Rue Henri Dunant, 94320 Thiais (France); Instituto de Física de São Carlos, Universidade de São Paulo, Av. Trabalhador São-Carlense, 400, São Carlos, SP (Brazil); Michalowicz, Alain, E-mail: michalov@u-pec.fr [Institut de Chimie et des Materiaux Paris Est, CNRS and Université Paris Est Créteil, 2 Rue Henri Dunant, 94320 Thiais (France); Moscovici, Jacques, E-mail: moscovic@u-pec.fr [Institut de Chimie et des Materiaux Paris Est, CNRS and Université Paris Est Créteil, 2 Rue Henri Dunant, 94320 Thiais (France); Pizani, Paulo Sergio, E-mail: pizani@df.ufscar.br [Departamento de Física, Universidade Federal de São Carlos, Rodovia Washington Luís, s/n, São Carlos, SP, 13565-905 (Brazil); Mastelaro, Valmor Roberto, E-mail: valmor@ifsc.usp.br [Instituto de Física de São Carlos, Universidade de São Paulo, Av. Trabalhador São-Carlense, 400, São Carlos, SP (Brazil)

    2016-08-15

    This paper reports on the structural characterization of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} (PBZT) ferroelectric ceramic compositions prepared by the conventional solid state reaction method. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used in the probing of the local structure of PBZT samples that exhibit a normal or relaxor ferroelectric behavior. They showed a considerable local disorder around Zr and Pb atoms in the samples of tetragonal or cubic long-range order symmetry. The intensity of the E(TO{sub 3}) mode in the Raman spectra of PBZT relaxor samples remains constant at temperatures lower than T{sub m}, which has proven the stabilization of the correlation process between nanodomains. - Graphical abstract: X-ray absorption measurements showed considerable local disorder around Zr and Pb atoms in the samples of tetragonal or cubic long-range order symmetry. The intensity of the E(TO{sub 3}) mode in the Raman spectra of PBZT relaxor samples remains constant at temperatures lower than T{sub m}, which has proven the stabilization of the correlation process between nanodomains. Display Omitted - Highlights: • Structural characterization of Pb{sub 1−x}Ba{sub x}Zr{sub 0.40}Ti{sub 0.60}O{sub 3} (PBZT) ferroelectric ceramic. • X-ray absorption and Raman spectroscopies were used to probe the structure of PBZT. • Dissymmetry of Zr and Pb sites was observed in samples long-range cubic symmetry. • Local disorder in all PBZT samples through the observation of Raman active modes.

  10. Structural and chemical reactivity modifications of a cobalt perovskite induced by Sr-substitution. An in situ XAS study

    International Nuclear Information System (INIS)

    Hueso, Jose L.; Holgado, Juan P.; Pereñíguez, Rosa; Gonzalez-DelaCruz, V.M.; Caballero, Alfonso

    2015-01-01

    LaCoO 3 and La 0.5 Sr 0.5 CoO 3−δ perovskites have been studied by in situ Co K-edge XAS. Although the partial substitution of La(III) by Sr(II) species induces an important increase in the catalytic oxidation activity and modifies the electronic state of the perovskite, no changes could be detected in the oxidation state of cobalt atoms. So, maintaining the electroneutrality of the perovskite requires the generation of oxygen vacancies in the network. The presence of these vacancies explains that the substituted perovskite is now much more reducible than the original LaCoO 3 perovskite. As detected by in situ XAS, after a consecutive reduction and oxidation treatment, the original crystalline structure of the LaCoO 3 perovskite is maintained, although in a more disordered state, which is not the case for the Sr doped perovskite. So, the La 0.5 Sr 0.5 CoO 3−δ perovskite submitted to the same hydrogen reduction treatment produces metallic cobalt, while as determined by in situ XAS spectroscopy the subsequent oxidation treatment yields a Co(III) oxide phase with spinel structure. Surprisingly, no Co(II) species are detected in this new spinel phase. - Highlights: • A Sr-substituted lanthanum cobalt perovskite has been prepared by spray pyrolysis. • It has been established that Co(III) cations are present in both perovskites. • LaCoO 3 is a less reducible phase than the substituted La 0.5 Sr 0.5 CoO 3−δ . • After reoxidation of reduced La 0.5 Sr 0.5 CoO 3−δ , a 100% Co(III) spinel is obtained

  11. Absorptive products

    International Nuclear Information System (INIS)

    Assarsson, P.G.; King, P.A.

    1976-01-01

    Applications for hydrophile gels produced by the radiation induced cross-linking in aqueous solution of polyethylene oxide and starch, as described in Norwegian patent 133501 (INIS RN 281494), such as sanitary napkins (diapers) and sanitary towels, are discussed. The process itself is also discussed and results, expressed as the percentage of insoluble gel and its absorptive capacity for saline solution as functions of the ratio of polyethylene oxide to starch and the radiation dose, are presented. (JIW)

  12. Gamma-ray burst spectra

    International Nuclear Information System (INIS)

    Teegarden, B.J.

    1982-01-01

    A review of recent results in gamma-ray burst spectroscopy is given. Particular attention is paid to the recent discovery of emission and absorption features in the burst spectra. These lines represent the strongest evidence to date that gamma-ray bursts originate on or near neutron stars. Line parameters give information on the temperature, magnetic field and possibly the gravitational potential of the neutron star. The behavior of the continuum spectrum is also discussed. A remarkably good fit to nearly all bursts is obtained with a thermal-bremsstrahlung-like continuum. Significant evolution is observed of both the continuum and line features within most events

  13. Dynamics of oxide growth on Pt nanoparticles electrodes in the presence of competing halides by operando energy dispersive X-Ray absorption spectroscopy

    KAUST Repository

    Minguzzi, Alessandro

    2018-03-17

    In this work we studied the kinetics of oxide formation and reduction on Pt nanoparticles in HClO4 in the absence and in the presence of Br− and Cl− ions. The study combines potential step methods (i.e. chronoamperometry and choronocoulometry) with energy dispersive X-ray absorption spectroscopy (ED-XAS), which in principle allows to record a complete XAS spectrum in the timescale of milliseconds. Here, the information on the charge state and on the atomic surrounding of the considered element provided by XAS was exploited to monitor the degree of occupancy of 5d states of Pt in the course of oxide formation and growth, and to elucidate the competing halide adsorption/desorption phenomena. Electrochemical methods and XAS agree on the validity of a log(t) depending growth of Pt oxide, that is significantly delayed in the presence of Cl− and Br− anions. In the proximity of formation of one monolayer, the growth is further slowed down.

  14. Dynamics of oxide growth on Pt nanoparticles electrodes in the presence of competing halides by operando energy dispersive X-Ray absorption spectroscopy

    KAUST Repository

    Minguzzi, Alessandro; Montagna, Linda; Falqui, Andrea; Vertova, Alberto; Rondinini, Sandra; Ghigna, Paolo

    2018-01-01

    In this work we studied the kinetics of oxide formation and reduction on Pt nanoparticles in HClO4 in the absence and in the presence of Br− and Cl− ions. The study combines potential step methods (i.e. chronoamperometry and choronocoulometry) with energy dispersive X-ray absorption spectroscopy (ED-XAS), which in principle allows to record a complete XAS spectrum in the timescale of milliseconds. Here, the information on the charge state and on the atomic surrounding of the considered element provided by XAS was exploited to monitor the degree of occupancy of 5d states of Pt in the course of oxide formation and growth, and to elucidate the competing halide adsorption/desorption phenomena. Electrochemical methods and XAS agree on the validity of a log(t) depending growth of Pt oxide, that is significantly delayed in the presence of Cl− and Br− anions. In the proximity of formation of one monolayer, the growth is further slowed down.

  15. Spin excitation and band-narrowing in Al{sub x}Ga{sub 1-x}As heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Miah, M. Idrish, E-mail: m.miah@griffith.edu.au [Department of Physics, University of Chittagong, Chittagong 4331 (Bangladesh)

    2010-11-01

    We studied the spin excitation in dependences of the applied electric field and lattice temperature (LT) via the measurements of the circularly polarized photoluminescence (CPPL) in Al{sub x}Ga{sub 1-x}As heterostructures (HSs). The intensity of CPPL was found to strongly depend on the electric field applied to the HSs. The CPPL was also found to enhance with decreasing LT. It was demonstrated that the observed LT dependence might be due to the LT-dependent band-gap shift of the HS materials.

  16. PySpline: A Modern, Cross-Platform Program for the Processing of Raw Averaged XAS Edge and EXAFS Data

    International Nuclear Information System (INIS)

    Tenderholt, Adam; Hedman, Britt; Hodgson, Keith O.

    2007-01-01

    PySpline is a modern computer program for processing raw averaged XAS and EXAFS data using an intuitive approach which allows the user to see the immediate effect of various processing parameters on the resulting k- and R-space data. The Python scripting language and Qt and Qwt widget libraries were chosen to meet the design requirement that it be cross-platform (i.e. versions for Windows, Mac OS X, and Linux). PySpline supports polynomial pre- and post-edge background subtraction, splining of the EXAFS region with a multi-segment polynomial spline, and Fast Fourier Transform (FFT) of the resulting k3-weighted EXAFS data

  17. Predicted electronic and structural properties of B{sub x}In{sub 1-x}As

    Energy Technology Data Exchange (ETDEWEB)

    Tayebi, N. [Laboratory of Applied Materials, University of Sidi Bel Abbes, 31 rue de Madagascar, Sidi Bel Abbes (Algeria); Benkabou, K., E-mail: kbenkabou@yahoo.fr [Laboratory of Applied Materials, University of Sidi Bel Abbes, 31 rue de Madagascar, Sidi Bel Abbes (Algeria); Aoumeur-Benkabou, F.Z. [Laboratory of Applied Materials, University of Sidi Bel Abbes, 31 rue de Madagascar, Sidi Bel Abbes (Algeria)

    2012-07-15

    Structural and electronic properties of the B{sub x}In{sub 1-x}As ternary alloy are studied using the tight binding method. The optical band gap bowing is calculated for the first time in the full range of Boron composition x. It is found to be strong. A small deviation from virtual crystal approximation is found for the bond length. New results on elastic constants are reported. The obtained results are in good agreement with the available data in the literature.

  18. Ultraviolet spectra of Mg in liquid helium

    International Nuclear Information System (INIS)

    Moriwaki, Y.; Morita, N.

    1999-01-01

    Emission and absorption spectra of Mg atoms implanted in liquid helium have been observed in the ultraviolet region. We have presented a model of exciplex formation of Mg-He 10 and found that this model is more suitable for understanding the dynamics in the 3s3p 1 P→3s 21 S transition than the bubble model. (orig.)

  19. 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.

    Science.gov (United States)

    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.

  20. Temperature dependence of the hydrated electron's excited-state relaxation. I. Simulation predictions of resonance Raman and pump-probe transient absorption spectra of cavity and non-cavity models

    Science.gov (United States)

    Zho, Chen-Chen; Farr, Erik P.; Glover, William J.; Schwartz, Benjamin J.

    2017-08-01

    We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron's resonance Raman O-H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time of the hydrated electron following photoexcitation. This is in sharp contrast to the predictions of the non-cavity model, where both the excited-state lifetime and hot ground-state cooling time are expected to decrease significantly with increasing temperature. These simulation-based predictions should be directly testable by the results of future time-resolved photoelectron spectroscopy experiments. Finally, the temperature-dependent differences in predicted excited-state lifetime and hot ground-state cooling time of the two models also lead to different predicted pump-probe transient absorption spectroscopy of the hydrated electron as a function of temperature. We perform such experiments and describe them in Paper II [E. P. Farr et al., J. Chem. Phys. 147, 074504 (2017)], and find changes in the excited-state lifetime and hot ground-state cooling time with temperature that match well with the predictions of the non-cavity model. In particular, the experiments

  1. Beta spectra. II-Positron spectra

    International Nuclear Information System (INIS)

    Grau, A.; Garcia-Torano, E.

    1981-01-01

    Using the Fermi theory of beta decay, the beta spectra for 30 positron emitters have been computed, introducing a correction factor for unique forbidden transitions. The spectra are ploted vs. energy, once normalised, and tabulated with the related Fermi functions. The average and median energies are calculated. (author)

  2. Rotational structure in molecular infrared spectra

    CERN Document Server

    di Lauro, Carlo

    2013-01-01

    Recent advances in infrared molecular spectroscopy have resulted in sophisticated theoretical and laboratory methods that are difficult to grasp without a solid understanding of the basic principles and underlying theory of vibration-rotation absorption spectroscopy. Rotational Structure in Molecular Infrared Spectra fills the gap between these recent, complex topics and the most elementary methods in the field of rotational structure in the infrared spectra of gaseous molecules. There is an increasing need for people with the skills and knowledge to interpret vibration-rotation spectra in many scientific disciplines, including applications in atmospheric and planetary research. Consequently, the basic principles of vibration-rotation absorption spectroscopy are addressed for contemporary applications. In addition to covering operational quantum mechanical methods, spherical tensor algebra, and group theoretical methods applied to molecular symmetry, attention is also given to phase conventions and their effe...

  3. Petroleum Science and Technology Institute with the TeXas Earth and Space Science (TXESS) Revolution

    Science.gov (United States)

    Olson, H. C.; Olson, J. E.; Bryant, S. L.; Lake, L. W.; Bommer, P.; Torres-Verdin, C.; Jablonowski, C.; Willis, M.

    2009-12-01

    The TeXas Earth and Space Science (TXESS) Revolution, a professional development program for 8th- thru 12th-grade Earth Science teachers, presented a one-week Petroleum Science and Technology Institute at The University of Texas at Austin campus. The summer program was a joint effort between the Jackson School of Geosciences and the Department of Petroleum and Geosystems Engineering. The goal of the institute was to focus on the STEM components involved in the petroleum industry and to introduce teachers to the larger energy resources theme. The institute kicked off with a welcoming event and tour of a green, energy-efficient home (LEED Platinum certified) owned by one of the petroleum engineering faculty. Tours of the home included an introduction to rainwater harvesting, solar energy, sustainable building materials and other topics on energy efficiency. Classroom topics included drilling technology (including a simulator lab and an overview of the history of the technology), energy use and petroleum geology, well-logging technology and interpretation, reservoir engineering and volumetrics (including numerous labs combining chemistry and physics), risk assessment and economics, carbon capture and storage (CO2 sequestration technology) and hydraulic fracturing. A mid-week field trip included visiting the Ocean Star offshore platform in Galveston, the Weiss Energy Hall at the Houston Museum of Science and Schlumberger (to view 3-D visualization technology) in Houston. Teachers remarked that they really appreciated the focused nature of the institute and especially found the increased use of mathematics both a tool for professional growth, as well as a challenge for them to use more math in their science classes. STEM integration was an important feature of the summer institute, and teachers found the integration of science (earth sciences, geophysics), technology, engineering (petroleum, chemical and reservoir) and mathematics particularly valuable. Pre

  4. Interaction of selenite with reduced Fe and/or S species: An XRD and XAS study.

    Science.gov (United States)

    Finck, Nicolas; Dardenne, Kathy

    2016-05-01

    In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (β-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered. Copyright © 2016. Published by Elsevier B.V.

  5. UMo nuclear fuels behaviour under heavy ion irradiation: a μ-XAS study

    International Nuclear Information System (INIS)

    Palancher, H.; Martin, P.; Dubois, S.; Valot, C.; Sabathier, C.; Palancher, H.; Nassif, V.; Proux, O.; Hazemann, J.L.; Wieschalla, N.; Petry, W.; Jarousse, C.

    2007-01-01

    Full text of publication follows. A worldwide program encourages the use of low enriched uranium (LEU, 235 U 235 U concentration up to 93 wt. %). Due to the decrease in 235 U enrichment for the conversion to LEU, the total density of uranium atoms in the fuel must be increased accordingly. To preserve the neutron flux, metallic uranium alloys could be the best fuel material. The fuel, which consists of UMo alloy spherical particles surrounded by an Al matrix (cf. Figure 1-A), is rolled between two aluminium claddings. Post-irradiation examinations of U-7 wt%Mo demonstrated its strong potentialities as fuel but they also pointed out its interaction with aluminium (cf. Figure 1-B). In certain cases this interaction can cause a break-away swelling of the plate. The aim of this project is the understanding of: - the phenomena driving the growth of the interaction layer. - the influence on interaction layer composition of limited adjunction of elements (silicon...) to the Al matrix. To overcome the difficulties inherent to the in-pile irradiated samples, an out-of-pile methodology (collaboration between CEA, FRM II and CERCA) has been developed based on heavy ion irradiation. This methodology enables to simulate the fission fragment damages using a 80 MeV iodine beam at the Maier Leibnitz laboratory (Garching, Germany). After irradiation, samples are characterised at micrometer scale by microscopy (SEM coupled with EDX) and X-Ray techniques (XRD and XAS). The irradiation (final dose: 2 x 10 17 at/cm 2 ) of undoped U-7 wt%Mo fuel plates leads to the formation of an interaction layer surrounding each fuel particles (cf. Figure 1-C). μ-XRD analysis performed at the ESRF (ID18f) showed only the presence of UAl 3 phase in the interaction layer. Same results have been obtained on in-pile irradiated fuel by Sears et al using neutron diffraction confirming the interest of the developed methodology. However the behaviour of the Mo atoms in the interaction layer could not be

  6. Composition-driven Cu-speciation and reducibility in Cu-CHA zeolite catalysts: a multivariate XAS/FTIR approach to complexity† †Electronic supplementary information (ESI) available: Sample description and synthesis details, experimental setup for in situ XAS and FTIR spectroscopy, details on the MCR-ALS method, details on DFT-assisted XANES simulations, details on the determination of N pure by PCA, MCR-ALS results for downsized and upsized component spaces, additional information to support the assignment of theoretical XANES curves, details on EXAFS analysis, details on IR spectral deconvolution. See DOI: 10.1039/c7sc02266b Click here for additional data file.

    Science.gov (United States)

    Martini, A.; Lomachenko, K. A.; Pankin, I. A.; Negri, C.; Berlier, G.; Beato, P.; Falsig, H.; Bordiga, S.; Lamberti, C.

    2017-01-01

    The small pore Cu-CHA zeolite is attracting increasing attention as a versatile platform to design novel single-site catalysts for deNOx applications and for the direct conversion of methane to methanol. Understanding at the atomic scale how the catalyst composition influences the Cu-species formed during thermal activation is a key step to unveil the relevant composition–activity relationships. Herein, we explore by in situ XAS the impact of Cu-CHA catalyst composition on temperature-dependent Cu-speciation and reducibility. Advanced multivariate analysis of in situ XANES in combination with DFT-assisted simulation of XANES spectra and multi-component EXAFS fits as well as in situ FTIR spectroscopy of adsorbed N2 allow us to obtain unprecedented quantitative structural information on the complex dynamics during the speciation of Cu-sites inside the framework of the CHA zeolite. PMID:29147509

  7. Biological Action Spectra (invited paper)

    Energy Technology Data Exchange (ETDEWEB)

    Gruijl, F.R. de

    2000-07-01

    Ultraviolet (UV) radiation induces a wide variety of biological responses: ranging in humans from well-known short-term effects like sunburn to long-term effects like skin cancer. The wavelength dependencies ('action spectra') of the responses can differ significantly, depending on the UV-targeted molecules (their absorption spectra), their localisation (transmission to the target depth) and the photochemical reactions involved (e.g. quantum yields, competing reaction). An action spectrum (e.g. of sunburn) is usually determined in a wavelength by wavelength analysis of the response. This is not always possible (e.g. in case of skin cancer), and an action spectrum may then be extracted mathematically from differences in responses to broadband UV sources of various spectral compositions (yielding 'biological spectral weights'). However, relative spectral weights may shift with exposure levels and contributions from different wavelengths may not always add up. Under these circumstances conventional analyses will yield different action spectra for different experimental conditions. (author)

  8. Structural properties and UV to NIR absorption spectra of metal-free phthalocyanine (H2Pc) thin films P. B. Thakor, P. N. Gajjar and A. R. Jani: Different reference systems in the study of structural properties of some simple liquid metals Shazia Bashir, M. S. Rafique, M. Khaleeq-ur-Rahman, Faizan-ul-Haq and B. R. Alvina: CO2 and Nd:YAG laser radiation induced damage in aluminium Smail Bougouffa: The study of atomic transitions by use of Numerov technique in schematic model

    Science.gov (United States)

    El-Nahass, M. M.; Farid, A. M.; Attia, A. A.; Ali, H. A. M.

    The structural properties and absorption spectra of H2Pc thin films have been studied. The films used in these studies were thermally evaporated on glass/quartz substrates with thickness ranging from 60 to 460 nm. The XRD studies of H2Pc thin films showed that the as-deposited films have a-form with monoclinic system. The mean crystallite size (L), the dislocation density (d) and the strain (x) were evaluated. The molecular structure of H2Pc thin films is confirmed by analysis of (FTIR) spectra. The surface morphology of H2Pc thin films was examined by scanning electron microscope. The absorption spectra of H2Pc recorded in the UV - VIS - IR region for the as-deposited and the annealed thin films of different thickness have been analyzed. The spectra showed two absorption bands namely the Q-band and the Soret (B)-band. The Q-band shows its characteristic splitting (Davydove splitting) with DQ = 0.21 eV. Values of some important optical parameters, namely optical absorption coefficient (a¢), molar extinction coefficient (emolar), half-band-width (Dl), electronic dipole strength (q2) and oscillator strength (f) were calculated. The fundamental and the onset of the indirect energy gaps were also determined as 2.47 and 1.4 eV, respectively.

  9. XAS AND XPS CHARACTERIZATION OF MERCURY BINDING ON BROMINATED ACTIVATED CARBON

    Science.gov (United States)

    Brominated powdered activated carbon sorbents have been shown to e quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when buring Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (X...

  10. Phase diagram of a two-dimensional liquid in GaAs/AlxGa1-xAs biased double quantum wells

    DEFF Research Database (Denmark)

    Timofeev, V. B.; Larionov, A. V.; Alessi, M. G.

    2000-01-01

    Photoluminescence (PL) and PL excitation (PLE) measurements have been performed in GaAs/AlxGa1-xAs biased double quantum well heterostructures. The recombination of electrons, e, with holes, h, located in the same or in two adjacent wells, has been investigated for different exciting power...

  11. Electron microscopic and optical investigations of the indium distribution GaAs capped InxGa1-xAs islands

    DEFF Research Database (Denmark)

    Woggon, U.; Langbein, Wolfgang Werner; Hvam, Jørn Märcher

    1997-01-01

    Results from a structural and optical analysis of buried InxGa1-xAs islands carried out after the process of GaAs overgrowth are presented. It is found that during the growth process, the indium concentration profile changes and the thickness of the wetting layer emanating from a Stranski-Krastan...

  12. The time-resolved and extreme conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the general-purpose EXAFS bending-magnet beamline BM23

    Energy Technology Data Exchange (ETDEWEB)

    Mathon, O., E-mail: mathon@esrf.fr; Beteva, A.; Borrel, J.; Bugnazet, D.; Gatla, S.; Hino, R.; Kantor, I.; Mairs, T. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Munoz, M. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Université Joseph Fourier, 1381 rue de la Piscine, BP 53, 38041 Grenoble Cedex 9 (France); Pasternak, S.; Perrin, F.; Pascarelli, S. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France)

    2015-10-17

    BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high-signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. It is a user-friendly facility featuring a high degree of automation, online EXAFS data reduction and a flexible sample environment.

  13. An assessment of some theoretical models used for the calculation of the refractive index of InXGa1-xAs

    Science.gov (United States)

    Engelbrecht, J. A. A.

    2018-04-01

    Theoretical models used for the determination of the refractive index of InXGa1-XAs are reviewed and compared. Attention is drawn to some problems experienced with some of the models. Models also extended to the mid-infrared region of the electromagnetic spectrum. Theoretical results in the mid-infrared region are then compared to previously published experimental results.

  14. Optimization of the confinement energy of quantum-wire states in T-shaped GaAs/AlxGa1-xAs structures

    DEFF Research Database (Denmark)

    Langbein, Wolfgang Werner; Gislason, Hannes; Hvam, Jørn Märcher

    1996-01-01

    We report on an optimization of the wire confinement energies of the confined electronic states at the T-shaped intersection of GaAs and AlxGa1-xAs quantum wells. These structures can be produced by the cleaved edge overgrowth technique. We present an analytical model for the confinement to give ...

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

    Science.gov (United States)

    Pedersen, Thomas G.

    2000-12-01

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

  16. Infrared spectra of jennite and tobermorite from first-principles

    Energy Technology Data Exchange (ETDEWEB)

    Vidmer, Alexandre, E-mail: alexandre@vidmer.com; Sclauzero, Gabriele; Pasquarello, Alfredo

    2014-06-01

    The infrared absorption spectra of jennite, tobermorite 14 Å, anomalous tobermorite 11 Å, and normal tobermorite 11 Å are simulated within a density-functional-theory scheme. The atomic coordinates and the cell parameters are optimized resulting in structures which agree with previous studies. The vibrational frequencies and modes are obtained for each mineral. The vibrational density of states is analyzed through extensive projections on silicon tetrahedra, oxygen atoms, OH groups, and water molecules. The coupling with the electric field is achieved through the use of density functional perturbation theory, which yields Born effective charges and dielectric constants. The simulated absorption spectra reproduce well the experimental spectra, thereby allowing for a detailed interpretation of the spectral features in terms of the underlying vibrational modes. In the far-infrared part of the absorption spectra, the interplay between Ca and Si related vibrations leads to differences which are sensitive to the calcium/silicon ratio of the mineral.

  17. X-ray absorption spectroscopic studies of the blue copper site: Metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin

    International Nuclear Information System (INIS)

    Shadle, S.E.; Penner-Hahn, J.E.; Schugar, H.J.; Hedman, B.; Hodgson, K.O.; Solomon, E.I.

    1993-01-01

    X-ray absorption spectra for the oxidized blue copper protein plastocyanin and several Cu(II) model complexes have been measured at both the Cu K-edge and the ligand K-edges (Cl and S) in order to elucidate the source of the small parallel hyperfine splitting in the EPR spectra of blue copper centers. Assignment and analysis of a feature in the Cu K-edge X-ray absorption spectrum at ∼8,987 eV as the Cu 1s → 4p + ligand-to-metal charge-transfer shakedown transition has allowed for quantitation of 4p mixing into the ground-state wave function as reflected in the 1s →3d (+4p) intensity at ∼8,979 eV. The results show that distorted tetrahedral (D 2d )CuCl 4 2- is characterized by z mixing, while plastocyanin has only Cu 4p xy mixing. Thus, the small parallel hyperfine splitting in the EPR spectra of D 2d CuCl 4 2- and of oxidized plastocyanin cannot be explained by 12% 4p z mixing into the 3d x 2 -y 2 orbital as had been previously postulated. Data collected at the Cl K-edge for CuCl 4 2- show that the intensity of the ligand pre-edge feature at ∼2,820 eV reflects the degree of covalency between the metal half-occupied orbital and the ligands. The data show that D 2d CuCl 4 2- is not unusually covalent. The source of the small parallel splitting in the EPR of D 2d CuCl 4 2- is discussed. Experiments at the S K-edge (∼2,470 eV) show that plastocyanin is characterized by a highly covalent Cu-S(cysteine) bond relative to the cupric-thiolate model complex [Cu(tet b)(o-SC 6 H 4 CO 2 )]·H 2 O. The XAS results demonstrate that the small parallel hyperfine splitting in the EPR spectra of blue copper sites reflects the high degree of covalency of the copper-thiolate bond. 34 refs., 12 figs., 3 tabs

  18. Approximation of Moessbauer spectra of metallic glasses

    International Nuclear Information System (INIS)

    Miglierini, M.; Sitek, J.

    1988-01-01

    Moessbauer spectra of iron-rich metallic glasses are approximated by means of six broadened lines which have line position relations similar to those of α-Fe. It is shown via the results of the DISPA (dispersion mode vs. absorption mode) line shape analysis that each spectral peak is broadened owing to a sum of Lorentzian lines weighted by a Gaussian distribution in the peak position. Moessbauer parameters of amorphous metallic Fe 83 B 17 and Fe 40 Ni 40 B 20 alloys are presented, derived from the fitted spectra. (author). 2 figs., 2 tabs., 21 refs

  19. Crystal-field spectra of fassaite from the Angra dos Reis meteorite

    Energy Technology Data Exchange (ETDEWEB)

    Mao, H K; Bell, P M; Virgo, D [Carnegie Institution of Washington, D.C. (USA)

    1977-06-01

    Fassaitic pyroxene from the Angra dos Reis meteorite has striking spectral properties. The /sup 57/Fe Moessbauer spectra show no Fe/sup 3 +/, and thus the absorption is thought to originate from a complex charge-transfer process. Intense absorption at 480 nm dominates the spectrum of the meteorite and may be important in the interpretation of telescope spectra of objects in space.

  20. Structure and dynamics in liquid water from x-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Wernet, Philippe

    2009-01-01

    Oxygen K-edge x-ray absorption spectra of water are discussed. The spectra of gas-phase water, liquid water and ice illustrate the sensitivity of oxygen K-edge x-ray absorption spectroscopy to hydrogen bonding in water. Transmission mode spectra of amorphous and crystalline ice are compared to x-ray Raman spectra of ice. The good agreement consolidates the experimental spectrum of crystalline ice and represents an incentive for theoretical calculations of the oxygen K-edge absorption spectrum of crystalline ice. Time-resolved infrared-pump and x-ray absorption probe results are finally discussed in the light of this structural interpretation.