Science.gov

Sample records for absorption edge spectra

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

    DTIC Science & Technology

    2016-03-31

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9675 Absorption-Edge-Modulated Transmission Spectra for Water Contaminant...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring...Unlimited Unclassified Unlimited 35 Samuel G. Lambrakos (202) 767-2601 Monitoring of contaminants associated with specific water resources using

  2. Multiple pre-edge structures in Cu K -edge x-ray absorption spectra of high- Tc cuprates revealed by high-resolution x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gougoussis, C.; Rueff, J.-P.; Calandra, M.; D'Astuto, M.; Jarrige, I.; Ishii, H.; Shukla, A.; Yamada, I.; Azuma, M.; Takano, M.

    2010-06-01

    Using high-resolution x-ray absorption spectroscopy and state-of-the-art electronic structure calculations we demonstrate that the pre-edge region at the Cu K edge of high- Tc cuprates is composed of several excitations invisible in standard x-ray absorption spectra. We consider in detail the case of Ca2-xCuO2Cl2 and show that the many pre-edge excitations (two for c -axis polarization, four for in-plane polarization and out-of-plane incident x-ray momentum) are dominated by off-site transitions and intersite hybridization. This demonstrates the relevance of approaches beyond the single-site model for the description of the pre edges of correlated materials. Finally, we show the occurrence of a doubling of the main edge peak that is most visible when the polarization is along the c axis. This doubling, that has not been seen in any previous absorption data in cuprates, is not reproduced by first-principles calculations. We suggest that this peak is due to many-body charge-transfer excitations while all the other visible far-edge structures are single particle in origin. Our work indicates that previous interpretations of the Cu K -edge x-ray absorption spectra in high- Tc cuprates can be profitably reconsidered.

  3. Zn K edge and O K edge x-ray absorption spectra of ZnO surfaces: implications for nanorods.

    PubMed

    Šipr, O; Rocca, F

    2011-08-10

    Zn K edge and O K edge x-ray absorption near-edge structure (XANES) spectra of ZnO surfaces are calculated. The difference between theoretical XANES for ZnO surfaces and ZnO bulk is then compared to the earlier observed differences between experimental XANES for ZnO nanostructures and ZnO bulk as taken from the literature. It follows from our calculations that the differences between the experimental XANES of bulk ZnO and nanocrystalline ZnO is not due to the enhanced role of the surfaces in nanostructures. Rather, the difference in XANES has to reflect differences in the local geometry around the photoabsorbing sites. The dependence of XANES of ZnO surfaces on the polarization of the incoming radiation is also investigated theoretically and found to be similar as in the bulk.

  4. K-edge x-ray absorption spectra of Cs and Xe

    SciTech Connect

    Gomilsek, J. Padeznik; Kodre, A.; Arcon, I.; Hribar, M.

    2003-10-01

    X-ray absorption spectrum of cesium vapor in the K-edge region is measured in a stainless steel cell. The spectrum is free of the x-ray absorption fine structure signal and shows small features analogous to those in the spectrum of the neighbor noble gas Xe. Although the large natural width of the K vacancy (>10 eV) washes out most of the details, fingerprints of multielectron excitations can be recognized at energies close to Dirac-Fock estimates of doubly excited states 1s4(d,p,s) and 1s3(d,p). Among these, the 1s3p excitation 1000 eV above the K edge in both spectra is the deepest double excitation observed so far. Within the K-edge profile, some resolution is recovered with numerical deconvolution of the spectra, revealing the coexcitation of the 5(p,s) electrons, and even the valence 6s electron in Cs. As in homologue elements, three-electron excitations, either as separate channels or as configuration admixtures are required to explain some spectral features in detail.

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

    PubMed

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5'-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'-monophosphate, and adenosine 5'-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. Calculation of optical and K pre-edge absorption spectra for ferrous iron of distorted sites in oxide crystals

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

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

    SciTech Connect

    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.

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

    SciTech Connect

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    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.

  9. General Method for Determination of the Surface Composition in Bimetallic Nanoparticle Catalysts from the L Edge X-ray Absorption Near-Edge Spectra

    SciTech Connect

    Wu, Tiapin; Childers, David; Gomez, Carolina; Karim, Ayman M.; Schweitzer, Neil; Kropf, Arthur; Wang, Hui; Bolin, Trudy B.; Hu, Yongfeng; Kovarik, Libor; Meyer, Randall; Miller, Jeffrey T.

    2012-10-08

    Bimetallic PtPd on silica nano-particle catalysts have been synthesized and their average structure determined by Pt L3 and Pd K-edge extended X-ray absorption finestructure (EXAFS) spectroscopy. The bimetallic structure is confirmed from elemental line scans by STEM for the individual 1-2 nm sized particles. A general method is described to determine the surface composition in bimetallic nanoparticles even when both metals adsorb, for example, CO. By measuring the change in the L3 X-ray absorption near-edge structure (XANES) spectra with and without CO in bimetallic particles and comparing these changes to those in monometallic particles of known size the fraction of surface atoms can be determined. The turnover rates (TOR) and neopentane hydrogenolysis and isomerization selectivities based on the surface composition suggest that the catalytic and spectroscopic properties are different from those in monometallic nano-particle catalysts. At the same neo-pentane conversion, the isomerization selectivity is higher for the PtPd catalyst while the TOR is lower than that of both Pt and Pd. As with the catalytic performance, the infrared spectra of adsorbed CO are not a linear combination of the spectra on monometallic catalysts. Density functional theory calculations indicate that the Pt-CO adsorption enthalpy increases while the Pd-CO bond energy decreases. The ability to determine the surface composition allows for a better understanding of the spectroscopic and catalytic properties of bimetallic nanoparticle catalysts.

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

    PubMed Central

    2015-01-01

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

  11. Comparison of x-ray absorption spectra between water and ice: New ice data with low pre-edge absorption cross-section

    SciTech Connect

    Sellberg, Jonas A.; Nilsson, Anders; Kaya, Sarp; Segtnan, Vegard H.; Chen, Chen; Tyliszczak, Tolek; Ogasawara, Hirohito; Nordlund, Dennis; Pettersson, Lars G. M.

    2014-07-21

    The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF{sub 2}(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

  12. Li K-edge X-ray absorption near edge structure spectra for a library of lithium compounds applied in lithium batteries

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Zuin, Lucia

    2017-01-01

    Lithium ion batteries (LIB) have achieved great success as energy supply systems in portable devices and in electrical vehicles. Identifying the local chemical structures of elemental lithium in lithium compounds is beneficial for improving understanding of battery components and performance. Herein, a library of Li K-edge X-ray absorption near edge structure (XANES) of lithium compounds relevant to Li-ion batteries is reported. Materials described include lithium metals (anode), Li-containing cathodes, electrolytes and solid electrolyte interphase (SEI). The results illustrate the characteristic spectral features stemming from the various electronic structures and chemical environment of lithium atoms for each and every possible battery component. XANES spectra of Sn based anode after discharging reveal the appearance of Li2CO3 on electrode surface. X-ray damage on sensitive lithium species is also assessed; the results reveal that more attention should be paid to irradiation effects to conduct XANES measurements for battery materials properly.

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

    PubMed

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

    2016-02-15

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

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

    PubMed

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

    2014-09-28

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

  15. Physical Properties of the Interstellar Medium Using High-resolution Chandra Spectra: O K-edge Absorption

    NASA Astrophysics Data System (ADS)

    Gatuzz, E.; García, J.; Mendoza, C.; Kallman, T. R.; Bautista, M. A.; Gorczyca, T. W.

    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 O = 0.70. The latter is given relative to the standard by Grevesse & 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 O = 9.2 × 1017 cm-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.

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

    SciTech Connect

    Gatuzz, E.; Mendoza, C.; García, J.; Kallman, T. R.; Bautista, M. A.; Gorczyca, T. W. E-mail: claudio@ivic.gob.ve E-mail: manuel.bautista@wmich.edu E-mail: timothy.r.kallman@nasa.gov

    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.

  17. Prediction of High-Valent Iron K-edge Absorption Spectra by Time-Dependent Density Functional Theory

    PubMed Central

    Chandrasekaran, P.; Stieber, S. Chantal E.; Collins, Terrence J.; Que, Lawrence; Neese, Frank; DeBeer, Serena

    2011-01-01

    In recent years a number of high-valent iron intermediates have been identified as reactive species in iron-containing metalloproteins. Inspired by the interest in these highly reactive species, chemists have synthesized Fe(IV) and Fe(V) model complexes with terminal oxo or nitrido groups, as well as a rare example of an Fe(VI)-nitrido species. In all these cases, X-ray absorption spectroscopy has played a key role in the identification and characterization of these species, with both the energy and intensity of the pre-edge features providing spectroscopic signatures for both the oxidation state and the local site geometry. Here we build on a time-dependent DFT methodology for the prediction of Fe K- pre-edge features, previously applied to ferrous and ferric complexes, and extend it to a range of Fe(IV), Fe(V) and Fe(VI) complexes. The contributions of oxidation state, coordination environment and spin state to the spectral features are discussed. These methods are then extended to calculate the spectra of the heme active site of P450 Compound II and the non-heme active site of TauD. The potential for using these methods in a predictive manner is highlighted. PMID:21956429

  18. Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method.

    PubMed

    Guo, Meiyuan; Sørensen, Lasse Kragh; Delcey, Mickaël G; Pinjari, Rahul V; Lundberg, Marcus

    2016-01-28

    The intensities and relative energies of metal K pre-edge features are sensitive to both geometric and electronic structures. With the possibility to collect high-resolution spectral data it is important to find theoretical methods that include all important spectral effects: ligand-field splitting, multiplet structures, 3d-4p orbital hybridization, and charge-transfer excitations. Here the restricted active space (RAS) method is used for the first time to calculate metal K pre-edge spectra of open-shell systems, and its performance is tested against on six iron complexes: [FeCl6](n-), [FeCl4](n-), and [Fe(CN)6](n-) in ferrous and ferric oxidation states. The method gives good descriptions of the spectral shapes for all six systems. The mean absolute deviation for the relative energies of different peaks is only 0.1 eV. For the two systems that lack centrosymmetry [FeCl4](2-/1-), the ratios between dipole and quadrupole intensity contributions are reproduced with an error of 10%, which leads to good descriptions of the integrated pre-edge intensities. To gain further chemical insight, the origins of the pre-edge features have been analyzed with a chemically intuitive molecular orbital picture that serves as a bridge between the spectra and the electronic structures. The pre-edges contain information about both ligand-field strengths and orbital covalencies, which can be understood by analyzing the RAS wavefunction. The RAS method can thus be used to predict and rationalize the effects of changes in both the oxidation state and ligand environment in a number of hard X-ray studies of small and medium-sized molecular systems.

  19. The Be K-edge in beryllium oxide and chalcogenides: soft x-ray absorption spectra from first-principles theory and experiment.

    PubMed

    Olovsson, W; Weinhardt, L; Fuchs, O; Tanaka, I; Puschnig, P; Umbach, E; Heske, C; Draxl, C

    2013-08-07

    We have carried out a theoretical and experimental investigation of the beryllium K-edge soft x-ray absorption fine structure of beryllium compounds in the oxygen group, considering BeO, BeS, BeSe, and BeTe. Theoretical spectra are obtained ab initio, through many-body perturbation theory, by solving the Bethe-Salpeter equation (BSE), and by supercell calculations using the core-hole approximation. All calculations are performed with the full-potential linearized augmented plane-wave method. It is found that the two different theoretical approaches produce a similar fine structure, in good agreement with the experimental data. Using the BSE results, we interpret the spectra, distinguishing between bound core-excitons and higher energy excitations.

  20. Experimental versus ab initio x-ray absorption of iron-doped zirconia: Trends in O K -edge spectra as a function of iron doping

    NASA Astrophysics Data System (ADS)

    Douma, D. H.; Ciprian, R.; Lamperti, A.; Lupo, P.; Cianci, E.; Sangalli, D.; Casoli, F.; Nasi, L.; Albertini, F.; Torelli, P.; Debernardi, A.

    2014-11-01

    We present an experimental study of x-ray absorption near edge structure (XANES) at L2 ,3,M2 ,3, and K edges of, respectively, Fe, Zr, and O in iron-doped zirconia (ZrO2:Fe ) for different Fe dopant concentrations x (from x ˜6 % to x ˜25 % at.) and make the comparison with ab initio simulations at the O K -edge. The x-ray magnetic circular dichroism (XMCD) measurements show no evidence of ferromagnetic (FM) order for all the analyzed samples in agreement with our ab initio simulations, which show an antiferromagnetic (AFM) order. We found that substituting Zr with Fe atoms leads to a radical change in the O K -edge XANES spectrum, especially in the pre-edge region where a pre-edge peak appears. This pre-edge peak is ascribed to dipole transitions from O 1 s to O 2 p states that are hybridized with the unoccupied Fe 3 d states. Both theoretical and experimental results reveal that the intensity of the pre-edge peak increases with Fe concentration, suggesting the increase of unoccupied Fe 3 d states. The increase of Fe concentration increases oxygen vacancies as required for charge neutrality and consequently improves AFM ordering. According to our first-principles calculations, the effect of one Fe atom is mostly localized in the first oxygen shell and vanishes as one moves far from it. Thus the increase of the O K -pre-edge peak with increasing Fe concentration is due to the increase of percentage of oxygen atoms that are near neighbors to Fe atoms.

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

    PubMed

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

    2010-06-07

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

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

    PubMed

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

    2011-05-12

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

  3. Preliminary optical design of a varied line-space spectrograph for the multi-channel detection of near-edge X-ray absorption fine structure (NEXAFS) spectra in the 280-550 eV energy range

    SciTech Connect

    Wheeler, B.S.; McKinney, W.R.; Hussain, Z.; Padmore, H.

    1996-07-01

    The optical design of a varied line-space spectrograph for the multi-channel recording of NEXAFS spectra in a single {open_quotes}snapshot{close_quotes} is proposed. The spectrograph is to be used with a bending magnet source on beamline 7.3.2 at the Advanced Light Source (ALS). Approximately 20 volts of spectra are simultaneously imaged across a small square of material sample at each respective K absorption edge of carbon, nitrogen, and oxygen. Photoelectrons emitted from the material sample will be collected by an electron imaging microscope, the view field of which determines the sampling size. The sample also forms the exit slit of the optical system. This dispersive method of NEXAFS data acquisition is three to four orders of magnitude faster than the conventional method of taking data point-to-point using scanning of the grating. The proposed design is presented along with the design method and supporting SHADOW raytrace analysis.

  4. Studies on the Structural Transformation of Pt Clusters with Adsorbed Hydrogen on α-Al2O3(0001) Using Multiple Scattering Approach to Pt L3-edge Polarized X-Ray Absorption Near Edge Structure Spectra for the Pt Cluster

    NASA Astrophysics Data System (ADS)

    Ohtani, Kunihiro

    1998-03-01

    The X-ray absorption near edge structure (XANES) or the Extended X-ray absorption fine structure (EXAFS) study with polarization dependence is useful for determining the structures of the metal clusters. We have calculated Pt L3-edge XANES spectra for various structures of Pt clusters with adsorbed hydrogen, such as the one-layer-thick raft, and the hemispherical and spherical structures on α-Al2O3(0001), using the full multiple scattering approach. Comparison of the calculated results with the experimental results have yielded important information. With an increase in the spherically symmetric character of Pt clusters, the influence of Pt-support interaction on the XANES spectra decreases, that is, the hydrogen-Pt interaction plays a dominant role in such cases. We expect that Pt clusters with the one-layer-thick raft, or hemispherical structures are on the top site of surface oxygen atoms.

  5. Urbach absorption edge in epitaxial erbium-doped silicon

    SciTech Connect

    Shmagin, V. B. Kudryavtsev, K. E.; Shengurov, D. V.; Krasilnik, Z. F.

    2015-02-07

    We investigate the dependencies of the photocurrent in Si:Er p-n junctions on the energy of the incident photons. The exponential absorption edge (Urbach edge) just below fundamental edge of silicon was observed in the absorption spectra of epitaxial Si:Er layers grown at 400–600 C. It is shown that the introduction of erbium significantly enhances the structural disorder in the silicon crystal which was estimated from the slope of the Urbach edge. We discuss the possible nature of the structural disorder in Si:Er and a new mechanism of erbium excitation, which does not require the presence of deep levels in the band gap of silicon.

  6. Electronic and Chemical State of Aluminum from the Single- (K) and Double-Electron Excitation (KLII&III, KLI) X-ray Absorption Near-Edge Spectra of α-Alumina, Sodium Aluminate, Aqueous Al(3+)·(H2O)6, and Aqueous Al(OH)4(-).

    PubMed

    Fulton, John L; Govind, Niranjan; Huthwelker, Thomas; Bylaska, Eric J; Vjunov, Aleksei; Pin, Sonia; Smurthwaite, Tricia D

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KLII&II) X-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral), are compared to aqueous species that have the same Al coordination symmetries, Al(3+)·6H2O (octahedral) and Al(OH)4(-) (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge; however, the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al(3+)·6H2O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region in the EXAFS spectra of the crystalline and aqueous standards. The K-edge spectra and K-edge energy positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge X-ray absorption near-edge spectra (XANES) reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&II and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method.

  7. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  8. Search for absorption edges in superexpansion bursts

    NASA Astrophysics Data System (ADS)

    in't Zand, Jean

    2013-09-01

    Our goal is to measure with the LETGS a series of bright type-I X-ray bursts with strong photospheric radius expansion ('superexpansion') to search for absorption edges due to the ashes of nuclear burning. We request a quick TOO, to be triggered by ISS-MAXI and Swift-BAT, with a total exposure time of 100 ks to obtain the detection of about 10 bursts.

  9. Creating semiconductor metafilms with designer absorption spectra

    PubMed Central

    Kim, Soo Jin; Fan, Pengyu; Kang, Ju-Hyung; Brongersma, Mark L.

    2015-01-01

    The optical properties of semiconductors are typically considered intrinsic and fixed. Here we leverage the rapid developments in the field of optical metamaterials to create ultrathin semiconductor metafilms with designer absorption spectra. We show how such metafilms can be constructed by placing one or more types of high-index semiconductor antennas into a dense array with subwavelength spacings. It is argued that the large absorption cross-section of semiconductor antennas and their weak near-field coupling open a unique opportunity to create strongly absorbing metafilms whose spectral absorption properties directly reflect those of the individual antennas. Using experiments and simulations, we demonstrate that near-unity absorption at one or more target wavelengths of interest can be achieved in a sub-50-nm-thick metafilm using judiciously sized and spaced Ge nanobeams. The ability to create semiconductor metafilms with custom absorption spectra opens up new design strategies for planar optoelectronic devices and solar cells. PMID:26184335

  10. Studies of OH - absorption and optical absorption spectra in LiNbO 3 : Mg, Ti crystals

    NASA Astrophysics Data System (ADS)

    Liu, Jianjun; Zhang, Wanlin; Zhang, Guangyin

    1996-02-01

    The OH - absorption spectra and the UV absorption edges of LiNbO 3 : Mg, Ti crystals have been measured. It is shown that Ti doping raises the Mg doping threshold level, and shifts the absorption edge towards longer wavelengths. The results can be explained by the formation of Mg Li2+Ti Nb4+ pairs after all antisite defects Nb Li have been replaced.

  11. Local structure and La L1 and L3-edge XANES spectra of lanthanum complex oxides.

    PubMed

    Asakura, Hiroyuki; Shishido, Tetsuya; Teramura, Kentaro; Tanaka, Tsunehiro

    2014-06-16

    La L1 and L3-edge X-ray absorption near-edge structure (XANES) of various La oxides were classified according to the local configuration of La. We found a correlation between both of the areas of the pre-edge peaks of the La L1-edge XANES spectra and the full width at half-maximum of white line of La L3-edge XANES spectra and the local configuration of La. Theoretical calculation of the XANES spectra and local density of states reveals the difference of La L1 and L3-edge XANES spectra of various La compounds is related to the p-d hybridization of the unoccupied band and broadening of the d band of La induced by the difference of local configuration. In addition, simplified bond angle analysis parameters defined by the angles of the La atom and the two adjacent oxygen atoms are correlated to the pre-edge peak intensity of the La L1-edge XANES spectra. These results indicate that quantitative analysis of La L1 and L3-edge XANES spectra could be an indicator of the local structure of La materials.

  12. On optimization of absorption-dispersion spectra

    NASA Astrophysics Data System (ADS)

    Hawranek, J. P.; Grabska, J.; Beć, K. B.

    2016-12-01

    A modified approach to the analysis of spectra of the complex electric permittivity of liquids in the Infrared region is presented. These spectra are derived from experimental spectra of the complex refractive index. Subsequently they are used to determine important secondary quantities, e.g. spectra of complex molecular polarizabilities and an integral property - the molar vibrational polarization. The accuracy of these quantities depends essentially on the accuracy of both components of the complex electric permittivity spectrum. In the proposed procedure, the spectra of the complex electric permittivity are approximated using the Classical Damped Harmonic Oscillator (CDHO) model for the description of individual bandshapes. The CDHO model defines both the real and imaginary part of the complex permittivity. The fitting procedure includes a simultaneous optimization of both the real and imaginary parts of the complex permittivity spectrum. A comparison of absorption-only curve fitting and the novel absorption-dispersion double curve fitting is presented; advantages of the new approach in accuracy, reliability and convergence time are pointed out. Due to the complexity of the problem, the choice was restricted to non-gradient methods of optimization. The performance of several gradientless algorithms was tested. Among numerous procedures the Powell General Least Squares Method Without Derivatives was found to be the most efficient. The reliability of obtained results of the band separatiovn process was tested on several simulated spectra of increasing complexity. The applicability of the developed approach to the analysis of exemplary experimental data was evaluated and discussed.

  13. High Resolution Spectra of Low Redshift Damped Lyalpha Absorption Systems

    NASA Astrophysics Data System (ADS)

    Cohen, R. D.; Beaver, E. A.; Junkkarinen, V. T.; Lyons, R. W.; Smith, H. E.

    1998-05-01

    We have been able to form a fairly complete picture of the galaxy responsible for the z_a=0.395 absorption line system in PKS 1229--021 by combining Keck HIRES and LRIS spectroscopy with observations taken with the Hubble Space Telescope. The image of the absorber is consistent with the inclined disk of a moderately luminous spiral galaxy. We have not been able to detect the continuum from this galaxy spectroscopically, but our LRIS spectra show emission from [O II] lambda3727 which can be interpreted to be indicative of star formation at the rate of a few M_⊙ per year. The HIRES spectra clearly show an ``edge--leading'' absorption profile. Prochaska and Wolfe have predicted that the velocity of the center of mass of the absorbing galaxy should fall near one edge of the absorption profile if the damped Lyalpha systems are due to the rotating disks of spiral galaxies. The [O II] emission velocity is consistent with this, but there is some ambiguity due to the doublet nature of the [O II] emission. Although the absorption lines of the abundant elements are saturated in the components which correspond to the H I absorption, we have been able to measure accurate column densities for Ca II, Ti II, and Mn II for comparison with the H I column density determined from low resolution HST/FOS spectra. The abundances are compatible with approximately 0.1 of solar, with little or no dust, but they are also consistent with lines of sight toward zeta Oph through warm interstellar clouds. HIRES observations of the z_a=0.692 absorption line system in 3CR 286 will also be discussed, after the data are fully analyzed. This work is part of the Goddard High Resolution Spectrograph Guaranteed Time Observations and is supported by NASA grant NAG5--1858 and the NSF.

  14. Terahertz absorption spectra of highly energetic chemicals

    NASA Astrophysics Data System (ADS)

    Slingerland, E. J.; Vallon, M. K.; Jahngen, E. G. E.; Giles, R. H.; Goyette, T. M.

    2010-04-01

    Research into absorption spectra is useful for detecting chemicals in the field. Each molecule absorbs a set of specific frequencies, which are dependent on the molecule's structure. While theoretical models are available for predicting the absorption frequencies of a particular molecule, experimental measurements are a more reliable method of determining a molecule's actual absorption behavior. The goal of this research is to explore chemical markers (absorption frequencies) that can be used to identify highly energetic molecules of interest to the remote sensing community. Particular attention was paid to the frequency ranges located within the terahertz transmission windows of the atmosphere. In addition, theoretical derivations, with the purpose of calculating the detection limits of such chemicals, will also be presented.

  15. Investigation of the mica x-ray absorption near-edge structure spectral features at the Al K-edge

    NASA Astrophysics Data System (ADS)

    Wu, Ziyu; Marcelli, A.; Cibin, G.; Mottana, A.; Della Ventura, G.

    2003-10-01

    Near-edge features of Al x-ray absorption near-edge structure (XANES) spectra in aluminosilicate compounds with mixed coordination number are usually assigned to a fourfold coordinated site contribution followed by a sixfold coordinated site contribution that is displaced towards higher energy because of the increasing ligand nucleus potentials, neglecting possible contributions due to bond distance variations and local geometrical distortion. Here we present and discuss the Al K-edge XANES spectra of synthetic micas with either fourfold coordinated Al (phlogopite), or with sixfold coordinated Al (polylithionite), as well as with mixed coordination (preiswerkite). Multiple scattering simulations of XANES spectra demonstrate that octahedral contributions may overlap the tetrahedral ones so that the lower energy structures in mixed coordination compounds may be associated with the octahedral sites. This unexpected behaviour can be described as due to the effect of a significant reduction of the ligand field strength (i.e. large local distortion and Al-O bond distances).

  16. Equilibria and absorption spectra of tryptophanase.

    PubMed

    Metzler, C M; Viswanath, R; Metzler, D E

    1991-05-25

    Tryptophanase (tryptophan: indole-lyase) from Escherichia coli has been isolated in the holoenzyme form and its absorption spectra and acid-base chemistry have been reevaluated. Apoenzyme has been prepared by dialysis against sodium phosphate and L-alanine and molar absorptivities of the coenzyme bands have been estimated by readdition of pyridoxal 5'-phosphate. The spectrophotometric titration curve, whose midpoint is at pH 7.6 in 0.1 M potassium phosphate buffers, indicates some degree of cooperativity in dissociation of a pair of protons. Resolution of the computed spectra of individual ionic forms of the enzyme with lognormal distribution curves shows that band shapes are similar to those of model Schiff bases and of aspartate aminotransferase. Using molar areas from the latter we estimated amounts of individual tautomeric species. In addition to ketoenamine and enolimine or covalent adduct the high pH form also appears to contain approximately 18% of a species with a dipolar ionic ring (protonated on the ring nitrogen and with phenolate -O-). We suggest that this may be the catalytically active form of the coenzyme in tryptophanase. The equilibrium between tryptophanase and L-alanine has also been reevaluated.

  17. Millimeter wave absorption spectra of biological samples

    SciTech Connect

    Gandhi, O.P.; Hagmann, M.J.; Hill, D.W.; Partlow, L.M.; Bush, L.

    1980-01-01

    A solid-state computer-controlled system has been used to make swept-frequency measurements of absorption of biological specimens from 26.5 to 90.0 GHz. A wide range of samples was used, including solutions of DNA and RNA, and suspensions of BHK-21/C13 cells, Candida albicans, C krusei, and Escherichia coli. Sharp spectra reported by other workers were not observed. The strong absorbance of water (10--30 dB/mm) caused the absorbance of all aqueous preparations that we examined to have a water-like dependence on frequency. Reduction of incident power (to below 1.0 microW), elimination of modulation, and control of temperature to assure cell viability were not found to significantly alter the water-dominated absorbance. Frozen samples of BHK-21/C13 cells tested at dry ice and liquid nitrogen temperatures were found to have average insertion loss reduced to 0.2 dB/cm but still showed no reproducible peaks that could be attributed to absorption spectra. It is concluded that the special resonances reported by others are likely to be in error.

  18. Edge Detection Techniques for Automatic Location of Spectra

    NASA Astrophysics Data System (ADS)

    Zarate, N.; Labrie, K.

    2012-09-01

    To improve the processing of multi-object or cross-dispersed spectroscopic data, especially for systems resulting in curved 2-D spectra, we have implemented in Python edge detection techniques widely used in the photo processing and remote sensing world. The software uses the discontinuity found in a spectral image to precisely locate each dispersed 2-D spectrum on the pixel array. A valid spectrum image edge is defined as continuous and sharp. To this end the best input data is a well illuminated flat field. The algorithm applies a discontinuity detection filter to the image. We find that a 3 × 3 Sobel kernel reliably produces easily traceable edges on our data. Some instruments produce data with large background noise. In those cases, a mild smoothing filter is first applied to reduce noise spikes that would otherwise confuse the edge tracing algorithm. The edges highlighted by the filtering are traced using the SciPy function label. Each edge is represented by a second degree polynomial that follows each slit edge. Currently the software assumes that the spectra are nearly horizontal or nearly vertical. This constraint can easily be lifted with the choice of a different convolution kernel.

  19. Neural Network Solutions to Optical Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Rosenbrock, Conrad

    2012-10-01

    Artificial neural networks have been effective in reducing computation time while achieving remarkable accuracy for a variety of difficult physics problems. Neural networks are trained iteratively by adjusting the size and shape of sums of non-linear functions by varying the function parameters to fit results for complex non-linear systems. For smaller structures, ab initio simulation methods can be used to determine absorption spectra under field perturbations. However, these methods are impractical for larger structures. Designing and training an artificial neural network with simulated data from time-dependent density functional theory may allow time-dependent perturbation effects to be calculated more efficiently. I investigate the design considerations and results of neural network implementations for calculating perturbation-coupled electron oscillations in small molecules.

  20. Optical absorption spectra of dications of carotenoids

    SciTech Connect

    Jeevarajan, J.A.; Wei, C.C.; Jeevarajan, A.S.; Kispert, L.D.

    1996-04-04

    Quantitative optical absorption spectra of the cation radicals and the dications of canthaxanthin (I), {beta}carotene (II), 7`-cyano-7`-ethoxycarbonyl-7`-apo-{beta}-carotene (III), and 7`,7`-dimethyl-7`-apo-{beta}-carotene (IV) in dichloromethane solution are reported. Exclusive formation of dications occurs when the carotenoids are oxidized with ferric chloride. Addition of neutral carotenoid to the dications results in equilibrium formation of cation radicals. Oxidation with iodine in dichloromethane affords only cation radicals; electrochemical oxidation under suitable conditions yields both dications and cation radicals. Values of the optical parameters depend on the nature of the oxidative medium. The oscillator strengths calculated for gas phase cation radicals and dications of I-IV using the INDO/S method show the same trend as the experimental values. 31 refs., 4 figs., 2 tabs.

  1. Cyclic voltammetry and near edge X-ray absorption fine structure spectroscopy at the Ag L3-edge on electrochemical halogenation of Ag layers on Au(111)

    NASA Astrophysics Data System (ADS)

    Endo, Osamu; Nakamura, Masashi

    2011-05-01

    One to three layers of Ag grown on a Au(111) electrode were studied by cyclic voltammetry in chloride and bromide solutions and by ex-situ near-edge X-ray absorption fine structure spectroscopy at the Ag L3-edge (Ag L3-NEXAFS). The one and two layers obtained by underpotential deposition exhibited reduced intensity at the absorption edge in the Ag L3-NEXAFS spectra, which suggests the gain of d-electrons in these layers. The cyclic voltammograms and the Ag L3-NEXAFS spectra indicate that the second and third layers of Ag halogenated at positive potentials, whereas the first layer remained in metallic form.

  2. Electronic absorption spectra from first principles

    NASA Astrophysics Data System (ADS)

    Hazra, Anirban

    Methods for simulating electronic absorption spectra of molecules from first principles (i.e., without any experimental input, using quantum mechanics) are developed and compared. The electronic excitation and photoelectron spectra of ethylene are simulated, using the EOM-CCSD method for the electronic structure calculations. The different approaches for simulating spectra are broadly of two types---Frank-Condon (FC) approaches and vibronic coupling approaches. For treating the vibrational motion, the former use the Born-Oppenheimer or single surface approximation while the latter do not. Moreover, in our FC approaches the vibrational Hamiltonian is additively separable along normal mode coordinates, while in vibronic approaches a model Hamiltonian (obtained from ab initio electronic structure theory) provides an intricate coupling between both normal modes and electronic states. A method called vertical FC is proposed, where in accord with the short-time picture of molecular spectroscopy, the approximate excited-state potential energy surface that is used to calculate the electronic spectrum is taken to reproduce the ab initio potential at the ground-state equilibrium geometry. The potential energy surface along normal modes may be treated either in the harmonic approximation or using the full one-dimensional potential. Systems with highly anharmonic potential surfaces can be treated and expensive geometry optimizations are not required, unlike the traditional FC approach. The ultraviolet spectrum of ethylene between 6.2 and 8.7 eV is simulated using vertical FC. While FC approaches for simulation are computationally very efficient, they are not accurate when the underlying approximations are unreasonable. Then, vibronic coupling model Hamiltonians are necessary. Since these Hamiltonians have an analytic form, they are used to map the potential energy surfaces and understand their topology. Spectra are obtained by numerical diagonalization of the Hamiltonians. The

  3. Computed survey spectra of 2-5 micron atmospheric absorption

    NASA Astrophysics Data System (ADS)

    Leslie, D. H.; Lebow, P. S.

    1983-08-01

    Computed high resolution survey spectra of atmospheric absorption coefficient vs wavenumber are presented covering the wavelength region 2-5 micrometers. The 1980 AFGL atmospheric absorption parameter compilation was employed with a mid-latitude, sea-level atmospheric model.

  4. Anomalous atmospheric absorption spectra due to water dimer

    NASA Astrophysics Data System (ADS)

    Cai, Peipei; Zhang, Hansheng; Shen, Shanxiong; Cheng, I.-Shan

    1986-11-01

    The anomalous atmospheric absorption spectra in the window wavelength region of 8-14 microns have been suggested due to the water dimer. Based on laboratory measurements, water continuum CO2 laser absorption spectra and a resonance absorption line due to the weak local wave vapor pure rotational transition have been reported. The equilibrium concentration of water dimers in the atmosphere, the electronic binding energy and the theoretical calculations for absorption attenuation have been obtained in agreement with published data.

  5. Carbon K-edge Spectra of Carbonate Minerals

    SciTech Connect

    Brandes, J.; Wirick, S; Jacobsen, C

    2010-01-01

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

  6. Photonic band-edge-induced enhancement in absorption and emission

    NASA Astrophysics Data System (ADS)

    Ummer, Karikkuzhi Variyath; Vijaya, Ramarao

    2015-01-01

    An enhancement in photonic band-edge-induced absorption and emission from rhodamine-B dye doped polystyrene pseudo gap photonic crystals is studied. The band-edge-induced enhancement in absorption is achieved by selecting the incident angle of the excitation beam so that the absorption spectrum of the emitter overlaps the photonic band edge. The band-edge-induced enhancement in emission, on the other hand, is possible with and without an enhancement in band-edge-induced absorption, depending on the collection angle of emission. Through a simple set of measurements with suitably chosen angles for excitation and emission, we achieve a maximum enhancement of 70% in emission intensity with band-edge-induced effects over and above the intrinsic emission in the case of self-assembled opals. This is a comprehensive effort to interpret tunable lasing in opals as well as to predict the wavelength of lasing arising as a result of band-edge-induced distributed feedback effects.

  7. Optical Absorption Spectra of Hydrous Wadsleyite to 32 GPa

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Goncharov, A. F.; Jacobsen, S. D.; Bina, C. R.; Frost, D. J.

    2009-05-01

    Optical absorption spectra of high-pressure minerals can be used as indirect tools to calculate radiative conductivity of the Earth's interior [e.g., 1]. Recent high-pressure studies show that e.g. ringwoodite, γ-(Mg,Fe)2SiO4, does not become opaque in the near infrared and visible region, as previously assumed, but remains transparent to 21.5 GPa [2]. Therefore, it has been concluded that radiative heat transfer does not necessarily become blocked at high pressures of the mantle and ferromagnesian minerals actually could contribute to the heat flow in the Earth's interior [2]. In this study we use gem-quality single-crystals of hydrous Fe-bearing wadsleyite, β-(Mg,Fe)2SiO4, that were synthesized at 18 GPa and 1400 °C in a multianvil apparatus. Crystals were analyzed by Mössbauer and Raman spectroscopy, electron microprobe analysis and single-crystal X-ray diffraction. For absorption measurements a double-polished 50 μm sized single-crystal of wadsleyite was loaded in a diamond-anvil cell with neon as pressure medium. Optical absorption spectra were recorded at ambient conditions as well as up to 32 GPa from 400 to 50000 cm-1. At ambient pressure the absorption spectrum reveals two broad bands at - 10000 cm-1 and -15000 cm-1, and an absorption edge in the visible-ultraviolet range. With increasing pressure the absorption spectrum changes, both bands continuously shift to higher frequencies as has been observed for ringwoodite [2], but is contrary to earlier presumptions for wadsleyite [3]. Here, we will discuss band assignment along with the influence of iron, compare our results to previous absorption studies of mantle materials [2], and analyze possible implications for radiative conductivity of the transition zone. References: [1] Goncharov et al. (2008), McGraw Yearbook Sci. Tech., 242-245. [2] Keppler & Smyth (2005), Am. Mineral., 90 1209-1212. [3] Ross (1997), Phys. Chem. Earth, 22 113-118.

  8. Photoabsorption spectra of potassium and rubidium near the K-edge

    SciTech Connect

    Azuma, Y.; Berry, H.G.; Cowan, P.L.

    1995-08-01

    We have used a high-temperature circulating heat-pipe absorption cell together with monochromatized X-ray beams at the X24A and X23A2 beam lines at the NSLS to obtain photoabsorption spectra of potassium and rubidium at their K- and KM-edges. The photon-energy ranges lay near 3600 eV and 15200 eV, respectively. We have also obtained first measurements of the LII and LIII edges in cesium. Although the K-edge photoabsorptions of the rare gases have been studied, there is little previous work on other atomic vapors. Most of the edges and resonance peaks that we observed have now been identified using Dirac Hartree-Fock calculations. As a check, we have compared these results with those obtained previously in closed-shell rare-gas absorption spectra. The absolute energies were obtained through a calibration of the X24A systems using measurements of several metal L-edges in the 3200-5000 eV energy range. We found that the 4p resonance in potassium is significantly enhanced compared with the corresponding situation in argon. Likewise, the 5p resonance in krypton is unresolved from the background ionization cross section, whereas it is well resolved in rubidium. As suggested by Amusia, these enhancements may be due to the enhanced potential seen in the excited state of the alkali systems as a result of the presence of an s-electron which reduces the nuclear shielding.

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

    SciTech Connect

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

    2017-01-01

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

  10. Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase.

    PubMed

    Godehusen, Kai; Richter, Tobias; Zimmermann, Peter; Wernet, Philippe

    2017-01-12

    Fe L-edge X-ray absorption spectra of gas-phase iron pentacarbonyl and ferrocene measured in total-ion yield mode are reported. Comparison to previously published spectra of free iron atoms and gaseous iron chloride demonstrates how the interplay of local atomic multiplet effects and orbital interactions in the metal-ligand bonds varies for the different systems. We find changes in the degree of metal-ligand covalency to be reflected in the measured 2p absorption onset. Orbital- or state-specific fragmentation is furthermore investigated in iron pentacarbonyl and ferrocene by analyzing the partial-ion-yield spectra at the Fe L-edge. Strong dependence of the yields of different fragments is observed in ferrocene in contrast to iron pentacarbonyl. This difference is attributed to the different degrees to which the 2p core hole is screened in the two systems and to which charge is rearranged in the Auger final states. We provide experimental benchmark spectra for new ab initio approaches for calculating metal L-edge absorption spectra of metal complexes.

  11. Collisionless absorption in sharp-edged plasmas

    SciTech Connect

    Gibbon, P. ); Bell, A.R. )

    1992-03-09

    The absorption of subpicosecond, obliquely incident laser light is studied using a 11/2D particle-in-cell code. Density scale lengths from {ital L}/{lambda}=0.01 to 2 and laser irradiances between {ital I}{lambda}{sup 2}=10{sup 14} and 10{sup 18} W cm{sup {minus}2} {mu}m{sup 2} are considered. Vacuum heating'' (F. Brunel, Phys. Rev. Lett. 59, 52 (1987)) dominates over resonance absorption for scale lengths {ital L}/{lambda}{lt}0.1, and is most efficient when {ital v}{sub osc}/{ital c}{congruent}3.1({ital L}/{lambda}){sup 2}. Absorbed energy is carried mainly by a superhot'' electron population with {ital U}{sub hot}{similar to}({ital I}{lambda}{sup 2}){sup 1/3--1/2}.

  12. Relativistic Effects Around Black Holes: Smearing Absorption Edges

    NASA Technical Reports Server (NTRS)

    Zhang, X. L.; Feng, Y. X.; Zhang, S. N.; Yao, Y.

    2002-01-01

    Broad iron absorption structures have been observed in the X-ray spectra of both AGNs and black hole X-ray binaries (BHXBs). A correctly modeled absorption structure can reveal the physical condition of the source, help to determine the continuum spectra and thus help to estimate other spectral lifes more accurately. The absorption structures are usually thought to be caused by the reflection of X-rays by the accretion disks around the central black holes, and the broadening can be a ttributed to the ionization states of the disk and relativistic effects.

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

    SciTech Connect

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

    2015-05-07

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

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

    PubMed

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

    2015-05-07

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

  15. A catalogue of absorption-line systems in QSO spectra

    NASA Astrophysics Data System (ADS)

    Ryabinkov, A. I.; Kaminker, A. D.; Varshalovich, D. A.

    2003-12-01

    We present a new catalog of absorption-line systems identified in the quasar spectra. It contains data on 821 QSOs and 8558 absorption systems comprising 16 139 absorption lines with measured redshifts in the QSO spectra. The catalog includes absorption-line systems consisting of lines of heavy elements, lines of neutral hydrogen, Lyman limit systems, damped Lyα absorption systems, and broad absorption-line systems. Using the data of the present catalog we also discuss redshift distributions of absorption-line systems. Tables 1 and 2 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/412/707

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

    PubMed

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

    2014-08-18

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

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

    PubMed Central

    2015-01-01

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

  18. Small copper clusters studied by x-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Oyanagi, H.; Sun, Z. H.; Jiang, Y.; Uehara, M.; Nakamura, H.; Yamashita, K.; Orimoto, Y.; Zhang, L.; Lee, C.; Fukano, A.; Maeda, H.

    2012-04-01

    The local structure of copper nanoparticles grown in organic solution by reducing Cu(II) hexafluoroacetylacetonate [Cu(hfac)2] was studied as-grown by the Cu K-edge x-ray absorption near-edge structure (XANES). Comparison of the experimental XANES spectra with reference materials indicated small copper clusters are formed by ligand-exchange with oleylamine and subsequent reducing by diphenylsilane. The multiple-scattering (MS) calculation for various model clusters consisting of 13-135 atoms suggests that small (13-19 atom) Cu clusters are stabilized without a large deformation.

  19. Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

    SciTech Connect

    Arber, J.M.; de Boer, E.; Garner, C.D.; Hasnain, S.S.; Wever, R. )

    1989-09-19

    Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure data confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.

  20. Probing the structure of iron at extreme conditions by X-ray absorption near-edge structure calculations

    NASA Astrophysics Data System (ADS)

    Raji, A. T.; Scandolo, S.; Härting, M.; Britton, D. T.

    2013-03-01

    We present the K-edge X-ray absorption near edge spectra of hexagonal-closed packed iron at pressure and temperature conditions relevant to Earth's mantle conditions. The calculated spectra have been obtained using the first-principles scheme based on the continued-fraction approach and norm-conserving pseudopotentials. The atomic configurations used for the X-ray absorption near edge spectroscopy calculations were obtained from classical molecular dynamics simulations, using an optimized embedded-atom potential. We compare our calculated spectra to recently available experiment results (R. Boehler, H.G. Musshoff, R. Ditz, G. Aquilanti, and A. Trapananti, Rev. Sci. Instrum. 80 (2009), pp. 045103-045108) and identify the main features of the spectra that may indicate onset of melting in iron.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  2. An investigation of a mathematical model for atmospheric absorption spectra

    NASA Technical Reports Server (NTRS)

    Niple, E. R.

    1979-01-01

    A computer program that calculates absorption spectra for slant paths through the atmosphere is described. The program uses an efficient convolution technique (Romberg integration) to simulate instrument resolution effects. A brief information analysis is performed on a set of calculated spectra to illustrate how such techniques may be used to explore the quality of the information in a spectrum.

  3. Deconvolution of CPM absorption spectra: A new technique

    NASA Astrophysics Data System (ADS)

    Jensen, Pablo

    1990-12-01

    We have found a new technique for deconvoluting absorption spectra obtained with the constant photocurrent method on hydrogenated amorphous silicon samples. We have shown that our method is simpler and more accurate than those used until now. Finally, examples of spectra deconvolution for one sample after various thermal treatments are provided.

  4. Mid-infrared FEL absorption spectra

    NASA Astrophysics Data System (ADS)

    Kozub, John A.; Feng, Bibo; Gabella, William E.

    2002-04-01

    The Vanderbilt Mark III FEL is a tunable source of high- intensity coherent mid-infrared radiation occurring as a train of picosecond pulses spaced 350ps apart. The laser beam is transported to each laboratory under vacuum, but is typically transmitted through some distance of atmosphere before reaching the target. Losses due to absorption by water vapor and CO2 can be large, and since the bandwidth of the FEL is several percent of the wavelength, the spectrum can be altered by atmospheric absorptions. In order to provide an accurate representation of the laser spectrum delivered to the target, and to investigate any non-linear effects associated with transport of the FEL beam, we have recorded the spectrum of the FEL output using a vacuum spectrometer positioned after measured lengths of atmosphere. The spectrometer is equipped with a linear pyroelectric array which provides the laser spectrum for each pulse. Absorption coefficients are being measured for laboratory air, averaged over the bandwidth of the FEL. The high peak powers of this Fel have induced damage in common infrared-transparent materials; we are also measuring damage thresholds for several materials at various wavelengths.

  5. Terahertz absorption spectra and potential energy distribution of liquid crystals.

    PubMed

    Chen, Zezhang; Jiang, Yurong; Jiang, Lulu; Ma, Heng

    2016-01-15

    In this work, the terahertz (THz) absorption spectra of a set of nematic liquid crystals were studied using the density functional theories (DFT). An accurate assignment of the vibrational modes corresponding to absorption frequencies were performed using potential energy distribution (PED) in a frequency range of 0-3 THz. The impacts of different core structures on THz absorption spectra were discussed. The results indicate that scope of application must be considered in the LC-based THz device designing. This proposed work may give a useful suggestion on the design of novel liquid crystal material in THz wave.

  6. Terahertz absorption spectra and potential energy distribution of liquid crystals

    NASA Astrophysics Data System (ADS)

    Chen, Zezhang; Jiang, Yurong; Jiang, Lulu; Ma, Heng

    2016-01-01

    In this work, the terahertz (THz) absorption spectra of a set of nematic liquid crystals were studied using the density functional theories (DFT). An accurate assignment of the vibrational modes corresponding to absorption frequencies were performed using potential energy distribution (PED) in a frequency range of 0-3 THz. The impacts of different core structures on THz absorption spectra were discussed. The results indicate that scope of application must be considered in the LC-based THz device designing. This proposed work may give a useful suggestion on the design of novel liquid crystal material in THz wave.

  7. Ab initio x-ray absorption near-edge structure study of Ti K-edge in rutile.

    PubMed

    Chaboy, J; Nakajima, N; Tezuka, Y

    2007-07-04

    This work reports a theoretical x-ray absorption near-edge structure (XANES) spectroscopy study at the Ti K-edge in TiO(2) rutile. We present detailed ab initio computations of the Ti K-edge XANES spectrum performed within the multiple-scattering framework. An extensive discussion is presented concerning the size of the cluster needed to reproduce the experimental spectrum, especially regarding the split main absorption line. In addition, the role of the exchange and correlation potential (ECP) in reproducing all the experimental XANES features is discussed. The best agreement between experimental data and computations is obtained by using real ECP potentials, i.e. the energy-dependent Dirac-Hara exchange potential, or by using only the real part of the energy-dependent Hedin-Lundqvist complex potential, together with an additional imaginary constant to account for the core-hole lifetime and the experimental resolution. The addition of the imaginary part of the HL potential worsens the agreement between the experimental and calculated spectra, indicating the failure of the complex part of the Hedin-Lundqvist ECP in accounting for the electron damping in these systems.

  8. Identification of THz absorption spectra of chemicals using neural networks

    NASA Astrophysics Data System (ADS)

    Shen, Jingling; Jia, Yan; Liang, Meiyan; Chen, Sijia

    2007-09-01

    Absorption spectra in the range from 0.2 to 2.6 THz of chemicals such as illicit drugs and antibiotics obtaining from Terahertz time-domain spectroscopy technique were identified successfully by artificial neural networks. Back Propagation (BP) and Self-Organizing Feature Map (SOM) were investigated to do the identification or classification, respectively. Three-layer BP neural networks were employed to identify absorption spectra of nine illicit drugs and six antibiotics. The spectra of the chemicals were used to train a BP neural network and then the absorption spectra measured in different times were identified by the trained BP neural network. The average identification rate of 76% was achieved. SOM neural networks, another important neural network which sorts input vectors by their similarity, was used to sort 60 absorption spectra from 6 illicit drugs. The whole network was trained by setting a 20×20 and a 16×16 grid, and both of them had given satisfied clustering results. These results indicate that it is feasible to apply BP and SOM neural networks model in the field of THz spectra identification.

  9. Demonstrating Absorption Spectra Using Commercially Available Incandescent Light Bulbs

    NASA Astrophysics Data System (ADS)

    Birriel, Jennifer J.

    In introductory astronomy courses, I typically introduce the three types of spectra: continuous, absorption line, and emission line. It is standard practice to use an ordinary incandescent light bulb to demonstrate the production of a continuous spectrum, and gas discharge tubes to demonstrate the production of an emission line spectrum. The concept of an absorption spectrum is more difficult for students to grasp. A variety of commercially available light bulbs can be used to demonstrate absorption spectra. Here I discuss the use of specialty incandescent light bulbs to demonstrate the phenomenon of absorption of the continuous spectrum produced by a hot tungsten filament. The bulbs examined include the GE Reveal bulb, yellow anti-insect lights, colored party bulbs, and an incandescent "black light" bulb. The bulbs can be used in a lecture or laboratory setting.

  10. Theoretical study on absorption and emission spectra of adenine analogues.

    PubMed

    Liu, Hongxia; Song, Qixia; Yang, Yan; Li, Yan; Wang, Haijun

    2014-04-01

    Fluorescent nucleoside analogues have attracted much attention in studying the structure and dynamics of nucleic acids in recent years. In the present work, we use theoretical calculations to investigate the structural and optical properties of four adenine analogues (termed as A1, A2, A3, and A4), and also consider the effects of aqueous solution and base pairing. The results show that the fluorescent adenine analogues can pair with thymine to form stable H-bonded WC base pairs. The excited geometries of both adenine analogues and WC base pairs are similar to the ground geometries. The absorption and emission maxima of adenine analogues are greatly red shifted compared with nature adenine, the oscillator strengths of A1 and A2 are stronger than A3 and A4 in both absorption and emission spectra. The calculated low-energy peaks in the absorption spectra are in good agreement with the experimental data. In general, the aqueous solution and base pairing can slightly red-shift both the absorption and emission maxima, and can increase the oscillator strengths of absorption spectra, but significantly decrease the oscillator strengths of A3 in emission spectra.

  11. Ultraviolet absorption spectra of metalorganic molecules diluted in hydrogen gas

    NASA Astrophysics Data System (ADS)

    Itoh, Hideo; Watanabe, Masanobu; Mukai, Seiji; Yajima, Hiroyoshi

    1988-12-01

    Ultraviolet absorption spectra of trimethyl gallium, triethyl gallium, and trimethyl aluminum diluted in hydrogen gas were measured as a function of the wavelength (185-350 nm) and the concentration of the molecules (4.8×10 -6 -1.6×10 -4 mol/liter). Their absorbances changed linearly with the concentration of the molecules, which allowed us to calculate the molar absorption coefficients of the molecules on the basis of the Beer-Lambert law.

  12. IR absorption spectra of cellulose obtained from ozonated wood

    NASA Astrophysics Data System (ADS)

    Mamleeva, N. A.; Autlov, S. A.; Kharlanov, A. N.; Bazarnova, N. G.; Lunin, V. V.

    2015-08-01

    The kinetic curves of ozone absorption by aspen wood were obtained. Processing of wood with peracetic acid gave cellulose samples. The yields of ozonated wood, water-soluble compounds, and cellulose were determined for the samples corresponding to different consumptions of ozone. The IR absorption spectra of wood and cellulose isolated from ozonated wood were analyzed. The supramolecular structure of cellulose can be changed by varying the conditions of wood ozonation.

  13. [Ultraviolet absorption spectra of iodine, iodide ion and triiodide ion].

    PubMed

    Wei, Yong-Ju; Liu, Cui-Ge; Mo, Li-Ping

    2005-01-01

    Ultraviolet absorption spectra of iodine I2, iodide ion I(-) and triiodide ion I3(-) were studied, and molar absorptivities of these species were determined. Absorption spectrum of I2 aqueous solution appears as an absorption peak at 203 nm with a molar absorptivity of 1.96 x 10(4) L x mol(-1) x cm(-1). Absorption spectrum of I(-) appears as two absorption peaks at 193 and 226 nm with molar absorptivities of 1.42 x 10(4) and 1.34 x 10(4) L x mol(-1) x cm(-1), respectively. When I2 aqueous solution is mixed with KI solution, two absorption peaks appear at 288 and 350 nm, respectively, indicating the formation of I3(-). Using saturation method, molar absorptivities of I3(-) at 288 and 350 nm were determined to be 3.52 x 10(4) and 2.32 x 10(4) L x mol(-1) x cm(-1), respectively.

  14. Effects of domain size on x-ray absorption spectra of boron nitride doped graphenes

    NASA Astrophysics Data System (ADS)

    Li, Xin; Hua, Weijie; Wang, Bo-Yao; Pong, Way-Faung; Glans, Per-Anders; Guo, Jinghua; Luo, Yi

    2016-08-01

    Doping is an efficient way to open the zero band gap of graphene. The control of the dopant domain size allows us to tailor the electronic structure and the properties of the graphene. We have studied the electronic structure of boron nitride doped graphenes with different domain sizes by simulating their near-edge X-ray absorption fine structure (NEXAFS) spectra at the N K-edge. Six different doping configurations (five quantum dot type and one phase-separated zigzag-edged type) were chosen, and N K-edge NEXAFS spectra were calculated with large truncated cluster models by using the density functional theory with hybrid functional and the equivalent core hole approximation. The opening of the band gap as a function of the domain size is revealed. We found that nitrogens in the dopant boundary contribute a weaker, red-shifted π* peak in the spectra as compared to those in the dopant domain center. The shift is related to the fact that these interfacial nitrogens dominate the lowest conduction band of the system. Upon increasing the domain size, the ratio of interfacial atom decreases, which leads to a blue shift of the π* peak in the total NEXAFS spectra. The spectral evolution agrees well with experiments measured at different BN-dopant concentrations and approaches to that of a pristine h-BN sheet.

  15. AKARI observations of ice absorption bands towards edge-on YSOs

    NASA Astrophysics Data System (ADS)

    Aikawa, Y.; Kamuro, D.; Sakon, I.; Itoh, Y.; Noble, J. A.; Pontoppidan, K. M., Fraser, H. J.; Terada, H.; Tamura, M.; Kandori, R.; Kawamura, A.; Ueno, M.

    2011-05-01

    Circumstellar disks and envelopes of low-mass YSOs contain significant amounts of ice. Such icy material will evolve to volatile components of planetary systems, such as comets in our solar system. In order to investigate the composition and evolution of circumstellar ice around low-mass YSOs, we have observed ice absorption bands towards eight YSOs ranging from class 0 to class II, among which seven are associated with edge-on disks. Slit-less spectroscopic observations are performed using the grism mode of Infrared Camera (IRC) on board AKARI, which enables us to obtain full NIR spectra from 2.5 μm to 5 μm, including the CO_2 band and the blue wing of the H_2O band, which are not accessible from the ground. We developed procedures to reduce the spectra of targets with nebulosity. The spectra are fitted with polynomial baselines to derive the absorption spectra. Then we fit the molecular absorption bands with the laboratory spectra from the database, considering the instrumental line profile and the spectral resolution of the dispersion element. Towards the Class 0-I sources, absorption bands of H_2O, CO_2, CO and XCN (OCN^-) are clearly detected. Weak features of 13CO_2, HDO, the C-H band, and gaseous CO are detected as well. OCS ice absorption is tentatively detected towards IRC-L1041-2. The detected features would mostly originate in the cold envelope, while CO gas and OCN^- could originate in the region close to the protostar. Towards class II stars, H_2O ice band is detected. We also detected H_2O ice, CO_2 ice and tentative CO gas features of the foreground component of class II stars.

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

    ERIC Educational Resources Information Center

    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…

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

    SciTech Connect

    Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.; Smith, Steven C.; McNamara, Bruce K.; Buck, Edgar C.; Eiden, Gregory C.; Duffin, Andrew M.

    2016-03-01

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

  18. Uncertainty analysis for absorption and first-derivative EPR spectra.

    PubMed

    Tseitlin, Mark; Eaton, Sandra S; Eaton, Gareth R

    2012-11-01

    Electron paramagnetic resonance (EPR) experimental techniques produce absorption or first-derivative spectra. Uncertainty analysis provides the basis for comparison of spectra obtained by different methods. In this study it was used to derive analytical equations to relate uncertainties for integrated intensity and line widths obtained from absorption or first-derivative spectra to the signal-to-noise ratio (SNR), with the assumption of white noise. Predicted uncertainties for integrated intensities and line widths are in good agreement with Monte Carlo calculations for Lorentzian and Gaussian lineshapes. Conservative low-pass filtering changes the noise spectrum, which can be modeled in the Monte Carlo simulations. When noise is close to white, the analytical equations provide useful estimates of uncertainties. For example, for a Lorentzian line with white noise, the uncertainty in the number of spins obtained from the first-derivative spectrum is 2.6 times greater than from the absorption spectrum at the same SNR. Uncertainties in line widths obtained from absorption and first-derivative spectra are similar. The impact of integration or differentiation on SNR and on uncertainties in fitting parameters was analyzed. Although integration of the first-derivative spectrum improves the apparent smoothness of the spectrum, it also changes the frequency distribution of the noise. If the lineshape of the signal is known, the integrated intensity can be determined more accurately by fitting the first-derivative spectrum than by first integrating and then fitting the absorption spectrum. Uncertainties in integrated intensities and line widths are less when the parameters are determined from the original data than from spectra that have been either integrated or differentiated.

  19. The absorption spectra of carbonates and their precursors.

    NASA Astrophysics Data System (ADS)

    Koike, C.; Chihara, H.; Suto, H.

    The carbonates calcite and dolomite have been discovered in the dust shells of evolved stars (Kemper et al. 2002) and young proto stars (Ceccarelli et al. 2002). The mechanism for carbonate formation with a aqueous or non-aqueous process were discussed in their papers. These processes have not yet been reproduced in a laboratory experiment. First of all, we measured the mass absorption spectra of varous carbonates were measured in the mid- and far-infrared region. These spectra show very strong and broad peaks in the far-infrared region. The calcite and dolomite have peaks at about 92 microns and 63 microns, respectively. The alternative process of carbonates has not yet been clear. We investigate the alternative process measuring the spectra of the precursors of carbonates. We will report the preliminary results and discuss about the alternative process comparing the measured spectra of the precursors with the observation.

  20. APM Z >=4 QSO Survey: Spectra and Intervening Absorption Systems

    NASA Astrophysics Data System (ADS)

    Storrie-Lombardi, L. J.; McMahon, R. G.; Irwin, M. J.; Hazard, C.

    1996-09-01

    The APM multicolor survey for bright z > 4 objects, covering 2500 deg^2^ of sky to m_r_ ~ 19, resulted in the discovery of 31 quasars with z ~> 4. High signal-to-noise optical spectrophotometry at 5 A resolution has been obtained for the 28 quasars easily accessible from the northern hemisphere. These spectra have been surveyed to create new samples of high-redshift Lyman-limit systems, damped Lyα absorbers, and metal absorption systems (e.g., C IV and Mg II). In this paper we present the spectra, together with line lists of the detected absorption systems. The QSOs display a wide variety of emission- and absorption-line characteristics, with five exhibiting broad absorption lines and one with extremely strong emission lines (BR 2248 - 1242). Eleven candidate damped Lyα absorption systems have been identified covering the redshift range 2.8 <= z <= 4.4 (eight with z > 3.5). An analysis of the measured redshifts of the high-ionization emission lines with the low-ionization lines shows them to be blueshifted by 430 +/- 60 km s^-1^. In a previous paper (by Storrie-Lombardi et al.) we discussed the redshift evolution of the Lyman limit systems cataloged here. In subsequent papers we will discuss the properties of the Lyα forest absorbers and the redshift and column density evolution of the damped Lyα absorbers.

  1. A method for normalization of X-ray absorption spectra

    SciTech Connect

    Weng, T.-C.; Waldo, G.S.; Penner-Hahn, J.E.

    2010-07-20

    Accurate normalization of X-ray absorption data is essential for quantitative analysis of near-edge features. A method, implemented as the program MBACK, to normalize X-ray absorption data to tabulated mass absorption coefficients is described. Comparison of conventional normalization methods with MBACK demonstrates that the new normalization method is not sensitive to the shape of the background function, thus allowing accurate comparison of data collected in transmission mode with data collected using fluorescence ion chambers or solid-state fluorescence detectors. The new method is shown to have better reliability and consistency and smaller errors than conventional normalization methods. The sensitivity of the new normalization method is illustrated by analysis of data collected during an equilibrium titration.

  2. Effect of pyridine on infrared absorption spectra of copper phthalocyanine.

    PubMed

    Singh, Sukhwinder; Tripathi, S K; Saini, G S S

    2008-02-01

    Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.

  3. AKARI observations of ice absorption bands towards edge-on young stellar objects

    NASA Astrophysics Data System (ADS)

    Aikawa, Y.; Kamuro, D.; Sakon, I.; Itoh, Y.; Terada, H.; Noble, J. A.; Pontoppidan, K. M.; Fraser, H. J.; Tamura, M.; Kandori, R.; Kawamura, A.; Ueno, M.

    2012-02-01

    Context. Circumstellar disks and envelopes of low-mass young stellar objects (YSOs) contain significant amounts of ice. Such icy material will evolve to become volatile components of planetary systems, such as comets in our solar system. Aims: To investigate the composition and evolution of circumstellar ice around low-mass young stellar objects (YSOs), we observed ice absorption bands in the near infrared (NIR) towards eight YSOs ranging from class 0 to class II, among which seven are associated with edge-on disks. Methods: We performed slit-less spectroscopic observations using the grism mode of the InfraRed Camera (IRC) on board AKARI, which enables us to obtain full NIR spectra from 2.5 μm to 5 μm, including the CO2 band and the blue wing of the H2O band, which are inaccessible from the ground. We developed procedures to carefully process the spectra of targets with nebulosity. The spectra were fitted with polynomial baselines to derive the absorption spectra. The molecular absorption bands were then fitted with the laboratory database of ice absorption bands, considering the instrumental line profile and the spectral resolution of the grism dispersion element. Results: Towards the class 0-I sources (L1527, IRC-L1041-2, and IRAS 04302), absorption bands of H2O, CO2, CO, and XCN are clearly detected. Column density ratios of CO2 ice and CO ice relative to H2O ice are 21-28% and 13-46%, respectively. If XCN is OCN-, its column density is as high as 2-6% relative to H2O ice. The HDO ice feature at 4.1 μm is tentatively detected towards the class 0-I sources and HV Tau. Non-detections of the CH-stretching mode features around 3.5 μm provide upper limits to the CH3OH abundance of 26% (L1527) and 42% (IRAS 04302) relative to H2O. We tentatively detect OCS ice absorption towards IRC-L1041-2. Towards class 0-I sources, the detected features should mostly originate in the cold envelope, while CO gas and OCN- could originate in the region close to the protostar

  4. Infrared absorption spectra of metal carbides, nitrides and sulfides

    NASA Technical Reports Server (NTRS)

    Kammori, O.; Sato, K.; Kurosawa, F.

    1981-01-01

    The infrared absorption spectra of 12 kinds of metal carbides, 11 kinds of nitrides, and 7 kinds of sulfides, a total of 30 materials, were measured and the application of the infrared spectra of these materials to analytical chemistry was discussed. The measurements were done in the frequency (wave length) range of (1400 to 400/cm (7 to 25 mu). The carbides Al4C3, B4C, the nitrides AlN, BN, Si3N4, WB, and the sulfides Al2S3, FeS2, MnS, NiS and PbS were noted to have specific absorptions in the measured region. The sensitivity of Boron nitride was especially good and could be detected at 2 to 3 micrograms in 300 mg of potassium bromide.

  5. EPR and electronic absorption spectra of copper bearing turquoise mineral

    NASA Astrophysics Data System (ADS)

    Sharma, K. B. N.; Moorthy, L. R.; Reddy, B. J.; Vedanand, S.

    1988-10-01

    Electron paramagnetic resonance and optical absorption spectra of turquoise have been studied both at room and low temperatures. It is concluded from the EPR spectra that the ground state of Cu 2+ ion in turquoise is 2A g(d x2- y2) and it is sited in an elongated rhombic octahedron (D 2π). The observed absorption bands at 14970 and 18354 cm -1 are assigned at 2A g→ 2B 1 g( dx2- y2→ xy) and 2A g→[ su2B 3g(d x 2-y 2→d yz) respectively assuming D 2π symmetry which are inconsistent with EPR studies. The three bands in the NIR region are attributed to combinations of fundamental modes of the H 2O molecule present in the sample.

  6. A theoretical approach to La L1-edge XANES spectra of La complex oxides and their local configuration

    NASA Astrophysics Data System (ADS)

    Asakura, Hiroyuki; Shishido, Tetsuya; Teramura, Kentaro; Tanaka, Tsunehiro

    2015-04-01

    The characteristic peaks (pre-edge peaks) in the La L1-edge X-ray absorption near edge structure (XANES) of various La complex oxides were analyzed by both experimental and theoretical approaches. The pre-edge peak areas are correlated with the bond angle analysis (BAA) parameter, which we proposed as an indicator of the centrosymmetry or disorder of the local configuration of the La site. The origin of the pre-edge peak and the parameterization criteria of the BAA parameter were evaluated using theoretical calculations based on molecular orbital theory and multiple scattering theory. The theoretical calculations showed that the origin of the pre-edge peak at the La L1-edge is electric dipole transition from 2s to unoccupied states generated by p-d hybridization. Medium-scale theoretical simulations of the La L1-edge XANES spectra of thousands of virtual La aqueous complex models verified that the parameterization criteria of the BAA parameter are applicable to local configuration analysis of La.

  7. A theoretical approach to La L(1)-edge XANES spectra of La complex oxides and their local configuration.

    PubMed

    Asakura, Hiroyuki; Shishido, Tetsuya; Teramura, Kentaro; Tanaka, Tsunehiro

    2015-04-28

    The characteristic peaks (pre-edge peaks) in the La L1-edge X-ray absorption near edge structure (XANES) of various La complex oxides were analyzed by both experimental and theoretical approaches. The pre-edge peak areas are correlated with the bond angle analysis (BAA) parameter, which we proposed as an indicator of the centrosymmetry or disorder of the local configuration of the La site. The origin of the pre-edge peak and the parameterization criteria of the BAA parameter were evaluated using theoretical calculations based on molecular orbital theory and multiple scattering theory. The theoretical calculations showed that the origin of the pre-edge peak at the La L1-edge is electric dipole transition from 2s to unoccupied states generated by p-d hybridization. Medium-scale theoretical simulations of the La L1-edge XANES spectra of thousands of virtual La aqueous complex models verified that the parameterization criteria of the BAA parameter are applicable to local configuration analysis of La.

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

    SciTech Connect

    Bartnik, A.; Wachulak, P.; Fiedorowicz, H.; Fok, T.; Jarocki, R.; Szczurek, M.

    2013-11-15

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

  9. Implications for High Energy Blazar Spectra from Intergalactic Absorption Calculations

    NASA Technical Reports Server (NTRS)

    Stecker, F

    2008-01-01

    Given a knowledge of the density spectra intergalactic low energy photons as a function of redshift, one can derive the intrinsic gamma-ray spectra and luminosities of blazars over a range of redshifts and look for possible trends in blazar evolution. Stecker, Baring & Summerlin have found some evidence hinting that TeV blazars with harder spectra have higher intrinsic TeV gamma-ray luminosities and indicating that there may be a correlation of spectral hardness and luminosity with redshift. Further work along these lines, treating recent observations of the blazers lES02291+200 and 3C279 in the TeV and sub-TeV energy ranges, has recently been explored by Stecker & Scully. GLAST will observe and investigate many blazars in the GeV energy range and will be sensitive to blazers at higher redshifts. I examine the implications high redshift gamma-ray absorption for both theoretical and observational blazer studies.

  10. Oscillator strength measurements of atomic absorption lines from stellar spectra

    NASA Astrophysics Data System (ADS)

    Lobel, Alex

    2011-05-01

    Herein we develop a new method to determine oscillator strength values of atomic absorption lines with state-of-the-art detailed spectral synthesis calculations of the optical spectrum of the Sun and of standard spectral reference stars. We update the log(gf) values of 911 neutral lines observed in the KPNO-FTS flux spectrum of the Sun and high-resolution echelle spectra (R = 80 000) of Procyon (F5 IV-V) and Eps Eri (K2 V) observed with large signal-to-noise (S/N) ratios of 2000 using the new Mercator-Hermes spectrograph at La Palma Observatory (Spain). We find for 483 Fe I, 85 Ni I, and 51 Si I absorption lines in the sample a systematic overestimation of the literature log(gf) values with central line depths below 15%. We employ a curve-of-growth analysis technique to test the accuracy of the new oscillator strength values and compare calculated equivalent line widths to the Moore, Minnaert, and Houtgast atlas of the Sun. The online SpectroWeb database at http://spectra.freeshell.org interactively displays the observed and synthetic spectra and provides the new log(gf) values together with important atomic line data. The graphical database is under development for stellar reference spectra of every spectral sub-class observed with large spectral resolution and S/N ratios.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  12. Optical absorption spectra of palladium doped gold cluster cations

    SciTech Connect

    Kaydashev, Vladimir E.; Janssens, Ewald Lievens, Peter

    2015-01-21

    Photoabsorption spectra of gas phase Au{sub n}{sup +} and Au{sub n−1}Pd{sup +} (13 ≤ n ≤ 20) clusters were measured using mass spectrometric recording of wavelength dependent Xe messenger atom photodetachment in the 1.9–3.4 eV photon energy range. Pure cationic gold clusters consisting of 15, 17, and 20 atoms have a higher integrated optical absorption cross section than the neighboring sizes. It is shown that the total optical absorption cross section increases with size and that palladium doping strongly reduces this cross section for all investigated sizes and in particular for n = 14–17 and 20. The largest reduction of optical absorption upon Pd doping is observed for n = 15.

  13. X-ray atomic absorption of cesium and xenon in the L-edge region

    SciTech Connect

    Kodre, A.; Padeznik Gomilsek, J.; Arcon, I.; Aquilanti, G.

    2010-08-15

    X-ray absorption of atomic cesium is measured in the L-edge region, using a beryllium-window cell for cesium vapor. For comparison, absorption in Xe gas in the same energy region is remeasured with improved signal-to-noise ratio. By combining deconvolution and modeling, the edge profiles are studied to determine the threshold energies and the shape of the edge apex with exponential slope of the high-energy flank. In both elements, multielectron excitations show the same basic ordering in compact groups, largely independent of the core-hole subshell, following the energy sequence of coexcited valence and subvalence orbitals. The main effect of 6s electron in Cs, apart from 2(s,p)6s excitation, is the enhancement of single- as well as some multielectron resonant channels. The spectra of both elements show the ''polarization effect'': a convex basic curvature of the L{sub 2} and L{sub 3} segments, a concave L{sub 1} segment. Previously, Kutzner demonstrated a convincing theoretical explanation of the effect on Xe in a relativistic random-phase approximation with relaxation involving overlap integrals with continuum [Rad. Phys. Chem. 70, 95 (2004)].

  14. Interstellar dust grain composition from high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, Lia

    2016-06-01

    X-ray light is sufficient to excite electrons from n=1 (K-shell) and n=2 (L-shell) energy levels of neutral interstellar metals, causing a sharp increase in the absorption cross-section. Near the ionization energy, the shape of the photoelectric absorption edge depends strongly on whether the atom is isolated or bound in molecules or minerals (dust). With high resolution X-ray spectroscopy, we can directly measure the state of metals and the mineral composition of dust in the interstellar medium. In addition, the scattering contribution to the X-ray extinction cross-section can be used to gauge grain size, shape, and filling factor. In order to fully take advantage of major advances in high resolution X-ray spectroscopy, lab measurements of X-ray absorption fine structure (XAFS) from suspected interstellar minerals are required. Optical constants derived from the absorption measurements can be used with Mie scattering or anomalous diffraction theory in order to model the full extinction cross-sections from the interstellar medium. Much like quasar spectra are used to probe other intergalactic gas, absorption spectroscopy of Galactic X-ray binaries and bright stars will yield key insights to the mineralogy and evolution of dust grains in the Milky Way.

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

    NASA Astrophysics Data System (ADS)

    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.

    2007-09-01

    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.

  16. Absorption Features in Spectra of Magnetized Neutron Stars

    SciTech Connect

    Suleimanov, V.; Hambaryan, V.; Neuhaeuser, R.; Potekhin, A. Y.; Pavlov, G. G.; Adelsberg, M. van; Werner, K.

    2011-09-21

    The X-ray spectra of some magnetized isolated neutron stars (NSs) show absorption features with equivalent widths (EWs) of 50-200 eV, whose nature is not yet well known.To explain the prominent absorption features in the soft X-ray spectra of the highly magnetized (B{approx}10{sup 14} G) X-ray dim isolated NSs (XDINSs), we theoretically investigate different NS local surface models, including naked condensed iron surfaces and partially ionized hydrogen model atmospheres, with semi-infinite and thin atmospheres above the condensed surface. We also developed a code for computing light curves and integral emergent spectra of magnetized neutron stars with various temperature and magnetic field distributions over the NS surface. We compare the general properties of the computed and observed light curves and integral spectra for XDINS RBS 1223 and conclude that the observations can be explained by a thin hydrogen atmosphere above the condensed iron surface, while the presence of a strong toroidal magnetic field component on the XDINS surface is unlikely.We suggest that the harmonically spaced absorption features in the soft X-ray spectrum of the central compact object (CCO) 1E 1207.4-5209 (hereafter 1E 1207) correspond to peaks in the energy dependence of the free-free opacity in a quantizing magnetic field, known as quantum oscillations. To explore observable properties of these quantum oscillations, we calculate models of hydrogen NS atmospheres with B{approx}10{sup 10}-10{sup 11} G(i.e., electron cyclotron energy E{sub c,e}{approx}0.1-1 keV) and T{sub eff} = 1-3 MK. Such conditions are thought to be typical for 1E 1207. We show that observable features at the electron cyclotron harmonics with EWs {approx_equal}100-200 eV can arise due to these quantum oscillations.

  17. Transient absorption spectra of the laser-dressed hydrogen atom

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-10-01

    We present a theoretical study of transient absorption spectra of laser-dressed hydrogen atoms, based on numerical solutions of the time-dependent Schrödinger equation. The timing of absorption is controlled by the delay between an extreme ultra violet (XUV) pulse and an infrared (IR) laser field. The XUV pulse is isolated and several hundred attoseconds in duration, which acts as a pump to drive the ground-state electron to excited p states. The subsequent interaction with the IR field produces dressed states, which manifest as sidebands between the 1s-np absorption spectra separated by one IR-photon energy. We demonstrate that the population of dressed states is maximized when the timing of the XUV pulse coincides with the zero crossing of the IR field, and that their energies can be manipulated in a subcycle time scale by adding a chirp to the IR field. An alternative perspective to the problem is to think of the XUV pulse as a probe to detect the dynamical ac Stark shifts. Our results indicate that the accidental degeneracy of the hydrogen excited states is removed while they are dressed by the IR field, leading to large ac Stark shifts. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 levels using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional three-level model that neglects the dynamical ac Stark shifts.

  18. State of manganese in the photosynthetic apparatus. 2. X-ray absorption edge studies on manganese in photosynthetic membrane

    SciTech Connect

    Kirby, J. A.; Goodin, D. B.; Wydrzynski, T.; Robertson, A. S.; Klein, M. P.

    1981-09-01

    X-ray absorption spectra at the Manganese K-edge are presented for spinach chloroplasts, and chloroplasts which have been Tris treated and hence unable to evolve oxygen. A significant change in the electronic environment of manganese is observed and is attributed to the release of manganese from the thylakoid membranes with a concomitant change in oxidation state. A correlation of the K-edge energy, defined as the energy at the first inflection point, with coordination charge has been established for a number of manganese compounds of known structure and oxidation state. In this study, comparison of the manganese K-edge energies of the chloroplast samples with the reference compounds places the average oxidation state of the chloroplasts between 2+ and 3+. Using the edge spectra for Tris treated membranes which were osmotically shocked to remove the released manganese, difference edge spectra were synthesized to approximate the active pool of manganese. Coordination charge predictions for this fraction are consistent with an average resting oxidation state higher than 2+. The shape at the edge is also indicative of heterogeneity of the manganese site, of low symmetry, or both.

  19. Photoacoustic spectroscopy of absorption edge for GaAsBi/GaAs nanowires grown on Si substrate

    NASA Astrophysics Data System (ADS)

    Zelewski, Szymon J.; Kopaczek, Jan; Linhart, Wojciech M.; Ishikawa, Fumitaro; Shimomura, Satoshi; Kudrawiec, Robert

    2016-10-01

    GaAsBi/GaAs nanowires (NWs) grown on Si substrate and proper reference samples have been studied by photoacoustic (PA) spectroscopy. It has been shown that PA signal originating from NWs is quite strong and can be easily identified in the PA spectra, as well as distinguished from the signal originating from the Si substrate. The absorption edge of GaAsBi/GaAs and GaAs NWs has been determined from the analysis of amplitude PA spectra to be 1.26 eV and 1.42 eV, respectively. These values are consistent with the band gap reduction resulting from the introduction of ˜2% Bi in bulk GaAsBi alloy. The presented results prove that, despite light scattering, which is typical for NWs, PA spectroscopy is an excellent tool to study the absorption edge in semiconductor NWs.

  20. Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Kositanont, Charnwit; Schwarzer, Klaus; Prietzel, Jörg; Hirunyatrakul, Phoosak; Kittikoon, Itthipon

    2012-01-01

    This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD) and Germanium detector (GeD), were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN) at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP) and particulate matter of less than 10 millionths of a meter (PM10) collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA) and principal component analysis (PCA) has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD) from typical marine sediments (TMS). PMID:23193498

  1. Ligand discrimination of myoglobin in solution: an iron L-edge X-ray absorption study of the active centre.

    PubMed

    Lange, Kathrin M; Golnak, Ronny; Bonhommeau, Sébastien; Aziz, Emad F

    2013-05-14

    Iron L-edge X-ray absorption spectra of the active centre of myoglobin in the met-form, in the reduced form and upon ligation to O2, CO, NO and CN are presented. The strength of ligation with the iron centre is finger-printed through the variation of the L3 : L2 intensity ratio. Charge Transfer Multiplet calculations are performed and give qualitative information about oxidation states as well as charge transfer.

  2. Observational Cosmology Using Absorption Lines in Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Aghaee, A.

    2016-09-01

    Distant, highly luminous quasars are important cosmological probes for a variety of astrophysical questions: the first generation of galaxies, the star formation history and metal enrichment in the early Universe, the growth of the first super massive black holes (SMBHs), the role of feedback from quasars and SMBHs in galaxy evolution, the epoch of reionization, etc. In addition, they are used as background illuminating source that reveal any object located by chance on the line of sight. I will present our group works in these issues that can be done using absorption lines in the quasar spectra.

  3. Optical absorption and scattering spectra of pathological stomach tissues

    NASA Astrophysics Data System (ADS)

    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.

  4. Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

    NASA Astrophysics Data System (ADS)

    Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

    2013-04-01

    Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

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

    SciTech Connect

    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.

  6. Study on Coloration Mechanism of Chinese Ancient Ceramics by X-ray Absorption Near-edge Structure

    NASA Astrophysics Data System (ADS)

    Peng, Y. H.; Xie, Z.; He, J. F.; Liu, Q. H.; Pan, Z. Y.; Cheng, W. R.; Wei, S. Q.

    2013-04-01

    The Fe K-edge X-ray absorption near-edge structure (XANES) spectra of a series of ceramic shards were measured by fluorescence mode to reveal the color-generating techniques of Chinese porcelain. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colors of the ceramics. The results indicate that the coloration for different ceramics depend on the valence states of iron as the main color element in glaze and the proportion of Fe2+ and Fe3+ was attributed to the baking technology. The findings provide important information for archaeologist on the coloration researches.

  7. Multiple-scattering approach to the x-ray-absorption spectra of 3d transition metals

    NASA Astrophysics Data System (ADS)

    Kitamura, Michihide; Muramatsu, Shinji; Sugiura, Chikara

    1986-04-01

    The x-ray-absorption near-edge structure (XANES) has been calculated for the 3d transition metals Cr, Fe, Ni, and Cu from a multiple-scattering approach within the muffin-tin-potential approximation, as a first step to studying the XANES for complicated materials. The muffin-tin potential is constructed via the Mattheiss prescription using the atomic data of Herman and Skillman. It is found that the XANES is sensitive to the potential used and that the calculated XANES spectra reproduce the number of peaks and their separations observed experimentally. The final spectra, including the lifetime-broadening effect, show the general features of each material. We emphasize that the multiple-scattering theory which can be applied to the disordered systems as well as the ordered ones may be promising as a tool to analyze the XANES of complicated materials.

  8. Influence of the local atomic structure in the X-ray absorption near edge spectroscopy of neptunium oxo ions.

    PubMed

    Lozano, Janeth M; Clark, David L; Conradson, Steven D; Den Auwer, Christophe; Fillaux, Clara; Guilaumont, Dominique; Keogh, D Webster; Mustre de Leon, Jose; Palmer, Phillip D; Simoni, Eric

    2009-11-28

    Experimental L(III) X-ray absorption near edge structure (XANES) spectra of the distorted octahedral neptunium oxo ions NpO(2)(OH)(4)(2-), NpO(4)(OH)(2)(3-), and NpO(6)(6-) are interpreted using relativistic full multiple scattering calculations of the X-ray absorption process. In this series of compounds, the neptunium cation exhibits two different oxidation states, VI and VII, with coordination spheres from di- to tetra oxo for the first two compounds. The comparison between calculated XANES spectra using the feff code and experimental ones shows that the main features in the spectra are determined by the local coordination around the actinide metal center. Furthermore, the projected density of electronic states (DOS) calculated from the XANES simulations using the feff code are compared to calculations using ADF code. They are both discussed in terms of molecular orbitals and qualitative evolution of bonding within this series of compounds.

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

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

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

  10. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

    PubMed Central

    Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

    2015-01-01

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

  11. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy.

    PubMed

    Silatani, Mahsa; Lima, Frederico A; Penfold, Thomas J; Rittmann, Jochen; Reinhard, Marco E; Rittmann-Frank, Hannelore M; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J; Chergui, Majed

    2015-10-20

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein's function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼ 200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump-probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center.

  12. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    PubMed

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states.

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

    SciTech Connect

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

    1996-01-10

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

  14. Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence-X-ray absorption near edge structure analysis

    NASA Astrophysics Data System (ADS)

    Polgári, Zs.; Meirer, F.; Sasamori, S.; Ingerle, D.; Pepponi, G.; Streli, C.; Rickers, K.; Réti, A.; Budai, B.; Szoboszlai, N.; Záray, G.

    2011-03-01

    X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors. XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl 2 or NiCl 2 treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α'-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.

  15. Qualitative Analysis of Liquid Hydrocarbon Mixtures by Absorption Spectra of Their Vapors

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.

    2016-11-01

    Absorption spectra of saturated vapors of hydrocarbons and their mixtures were studied near their first overtones. Absorption spectra of hydrocarbons in the liquid and vapor states were compared. The ability to analyze qualitatively the compositions of liquid hydrocarbon mixtures using absorption spectra of their vapors was demonstrated. Indirect evidence suggested that the nonlinear absorption as a function of concentration that was seen in liquid hydrocarbon mixtures was negligible in their vapors.

  16. Parametric distortion of the optical absorption edge of a magnetic semiconductor by a strong laser field

    SciTech Connect

    Nunes, O.A.C.

    1985-09-15

    The influence of a strong laser field on the optical absorption edge of a direct-gap magnetic semiconductor is considered. It is shown that as the strong laser intensity increases the absorption coefficient is modified so as to give rise to an absorption tail below the free-field forbidden gap. An application is made for the case of the EuO.

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

    NASA Astrophysics Data System (ADS)

    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. X-ray absorption of cadmium in the L-edge region

    SciTech Connect

    Padeznik Gomilsek, J.; Kodre, A.; Arcon, I.; Bratina, G.

    2011-11-15

    Atomic x-ray absorption of cadmium in the energy region of L edges was measured on the vapor of the element, in parallel with the absorption of Cd metal foil. Ionization thresholds of the three subshells are determined from the edge profiles, through the energies of pre-edge resonances and indium optical levels in the Z + 1 approximation. A purely experimental result, without extraneous data and with an accuracy of 0.2 eV, is the energy difference between the pre-edge resonance and the threshold energy of the metallic state. Some multielectron-excitation resonances are identified within 30 eV above the edges. The metal foil absorption is used for absolute determination of Cd absorption coefficient.

  19. Absorption and electroabsorption spectra of carotenoid cation radical and dication

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-05-01

    Radical cations and dications of two carotenoids astaxanthin and canthaxanthin were prepared by oxidation with FeCl 3 in fluorinated alcohols at room temperature. Absorption and electroabsorption (Stark effect) spectra were recorded for astaxanthin cations in mixed frozen matrices at temperatures about 160 K. The D 0→D 2 transition in cation radical is at 835 nm. The electroabsorption spectrum for the D 0→D 2 transition exhibits a negative change of molecular polarizability, Δ α=-1.2·10 -38 C·m 2/V (-105 A 3), which seems to originate from the change in bond order alternation in the ground state rather than from the electric field-induced interaction of D 1 and D 2 excited states. Absorption spectrum of astaxanthin dication is located at 715-717 nm, between those of D 0→D 2 in cation radical and S 0→S 2 in neutral carotenoid. Its shape reflects a short vibronic progression and strong inhomogeneous broadening. The polarizability change on electronic excitation, Δ α=2.89·10 -38 C·m 2/V (260 A 3), is five times smaller than in neutral astaxanthin. This value reflects the larger energetic distance from the lowest excited state to the higher excited states than in the neutral molecule.

  20. Excited state absorption spectra and intersystem crossing kinetics in diazanaphthalenes

    NASA Astrophysics Data System (ADS)

    Scott, Gary W.; Talley, Larry D.; Anderson, Robert W.

    1980-05-01

    Picosecond time-resolved, excited state absorption spectra in the visible following excitation at 355 nm are discussed for room temperature solutions of four diazanaphthalenes (DN)—quinoxaline (1,4-DN), quinazoline (1,3-DN), cinnoline (1,2-DN), and phthalazine (2,3-DN). Kinetics of singlet state decay are obtained by monitoring the decay of Sn←S1 bands. The intersystem crossing rate constant (kisc) is found to vary as kisc(1,4-DN)≳kisc(1,3-DN)≳kisc(1,2-DN). The kisc in phthalazine could not be determined from the weak, visible Sn←S1 absorption. Assuming rapid singlet vibrational relaxation and only minor effects due to energy gap variations, these experimental results agree with statistical limit predictions for the relative nonradiative rate. Calculations of the spin-orbit coupling matrix element βel= , using INDO wave functions, give the ordering βel(1,4-DN)≳βel(2,3-DN)≳βel(1,3-DN) ≳βel(1,2-DN).

  1. Communication: Near edge x-ray absorption fine structure spectroscopy of aqueous adenosine triphosphate at the carbon and nitrogen K-edges.

    PubMed

    Kelly, Daniel N; Schwartz, Craig P; Uejio, Janel S; Duffin, Andrew M; England, Alice H; Saykally, Richard J

    2010-09-14

    Near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen and carbon K-edges was used to study the hydration of adenosine triphosphate in liquid microjets. The total electron yield spectra were recorded as a function of concentration, pH, and the presence of sodium, magnesium, and copper ions (Na(+)/Mg(2+)/Cu(2+)). Significant spectral changes were observed upon protonation of the adenine ring, but not under conditions that promote π-stacking, such as high concentration or presence of Mg(2+), indicating that NEXAFS is insensitive to the phenomenon. Intramolecular inner-sphere association of Cu(2+) did create observable broadening of the nitrogen spectrum, whereas outer-sphere association with Mg(2+) did not.

  2. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    SciTech Connect

    Szilagyi, Robert K. . E-mail: Szilagyi@Montana.EDU; Schwab, David E.

    2005-04-29

    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.

  3. Estimation of damped oscillation associated spectra from ultrafast transient absorption spectra.

    PubMed

    van Stokkum, Ivo H M; Jumper, Chanelle C; Snellenburg, Joris J; Scholes, Gregory D; van Grondelle, Rienk; Malý, Pavel

    2016-11-07

    When exciting a complex molecular system with a short optical pulse, all chromophores present in the system can be excited. The resulting superposition of electronically and vibrationally excited states evolves in time, which is monitored with transient absorption spectroscopy. We present a methodology to resolve simultaneously the contributions of the different electronically and vibrationally excited states from the complete data. The evolution of the excited states is described with a superposition of damped oscillations. The amplitude of a damped oscillation cos(ωnt)exp(-γnt) as a function of the detection wavelength constitutes a damped oscillation associated spectrum DOASn(λ) with an accompanying phase characteristic φn(λ). In a case study, the cryptophyte photosynthetic antenna complex PC612 which contains eight bilin chromophores was excited by a broadband optical pulse. Difference absorption spectra from 525 to 715 nm were measured until 1 ns. The population dynamics is described by four lifetimes, with interchromophore equilibration in 0.8 and 7.5 ps. We have resolved 24 DOAS with frequencies between 130 and 1649 cm(-1) and with damping rates between 0.9 and 12 ps(-1). In addition, 11 more DOAS with faster damping rates were necessary to describe the "coherent artefact." The DOAS contains both ground and excited state features. Their interpretation is aided by DOAS analysis of simulated transient absorption signals resulting from stimulated emission and ground state bleach.

  4. Estimation of damped oscillation associated spectra from ultrafast transient absorption spectra

    NASA Astrophysics Data System (ADS)

    van Stokkum, Ivo H. M.; Jumper, Chanelle C.; Snellenburg, Joris J.; Scholes, Gregory D.; van Grondelle, Rienk; Malý, Pavel

    2016-11-01

    When exciting a complex molecular system with a short optical pulse, all chromophores present in the system can be excited. The resulting superposition of electronically and vibrationally excited states evolves in time, which is monitored with transient absorption spectroscopy. We present a methodology to resolve simultaneously the contributions of the different electronically and vibrationally excited states from the complete data. The evolution of the excited states is described with a superposition of damped oscillations. The amplitude of a damped oscillation cos(ωnt)exp(-γnt) as a function of the detection wavelength constitutes a damped oscillation associated spectrum DOASn(λ) with an accompanying phase characteristic φn(λ). In a case study, the cryptophyte photosynthetic antenna complex PC612 which contains eight bilin chromophores was excited by a broadband optical pulse. Difference absorption spectra from 525 to 715 nm were measured until 1 ns. The population dynamics is described by four lifetimes, with interchromophore equilibration in 0.8 and 7.5 ps. We have resolved 24 DOAS with frequencies between 130 and 1649 cm-1 and with damping rates between 0.9 and 12 ps-1. In addition, 11 more DOAS with faster damping rates were necessary to describe the "coherent artefact." The DOAS contains both ground and excited state features. Their interpretation is aided by DOAS analysis of simulated transient absorption signals resulting from stimulated emission and ground state bleach.

  5. Bound excitons and many-body effects in x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Draxl, Claudia

    2015-11-01

    We study x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers (SAMs), investigating excitations from the nitrogen K edge. Azobenzene with H-termination and functionalized with CF3 groups is considered. The Bethe-Salpeter equation is employed to compute the spectra, including excitonic effects, and to determine the character of the near-edge resonances. Our results indicate that core-edge excitations are intense and strongly bound: their binding energies range from about 6 to 4 eV, going from isolated molecules to densely-packed SAMs. Electron-hole correlation rules these excitations, while the exchange interaction plays a negligible role.

  6. Local electronic structure of aqueous zinc acetate: oxygen K-edge X-ray absorption and emission spectroscopy on micro-jets.

    PubMed

    Golnak, Ronny; Atak, Kaan; Suljoti, Edlira; Hodeck, Kai F; Lange, Kathrin M; Soldatov, Mikhail A; Engel, Nicholas; Aziz, Emad F

    2013-06-07

    Oxygen K-edge X-ray absorption, emission, and resonant inelastic X-ray scattering spectra were measured to site selectively gain insights into the electronic structure of aqueous zinc acetate solution. The character of the acetate ion and the influence of zinc and water on its local electronic structure are discussed.

  7. Evaluation of iron-containing carbon nanotubes by near edge X-ray absorption technique

    NASA Astrophysics Data System (ADS)

    Osorio, A. G.; Bergmann, C. P.

    2015-10-01

    The synthesis of carbon nanotubes (CNTs) via Chemical Vapor Deposition method with ferrocene results in CNTs filled with Fe-containing nanoparticles. The present work proposes a novel route to characterize the Fe phases in CNTs inherent to the synthesis process. CNTs were synthesized and, afterwards, the CNTs were heat treated at 1000 °C for 20 min in an inert atmosphere during a thermogravimetric experiment. X-Ray Absorption Spectroscopy (XAS) experiments were performed on the CNTs before and after the heat treatment and, also, during the heat treatment, e.g., in situ tests were performed while several Near-Edge X-Ray Absorption (XANES) spectra were collected during the heating of the samples. The XAS technique was successfully applied to evaluate the phases encapsulated by CNTs. Phase transformations of the Fe-based nanoparticles were also observed from iron carbide to metallic iron when the in situ experiments were performed. Results also indicated that the applied synthesis method guarantees that Fe phases are not oxidize. In addition, the results show that heat treatment under inert atmosphere can control which phase remains encapsulated by the CNTs.

  8. Shift of optical absorption edge in SnO2 films with high concentrations of nitrogen grown by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Jiang, Jie; Lu, Yinmei; Meyer, Bruno K.; Hofmann, Detlev M.; Eickhoff, Martin

    2016-06-01

    The optical and electrical properties of n-type SnO2 films with high concentrations of nitrogen (SnO2:N) grown by chemical vapor deposition are studied. The carrier concentration increases from 4.1 × 1018 to 3.9 × 1019 cm-3 and the absorption edge shifts from 4.26 to 4.08 eV with increasing NH3 flow rate. Typical Urbach tails were observed from the absorption spectra and the Urbach energy increases from 0.321 to 0.526 eV with increasing NH3 flow rate. An "effective" absorption edge of about 4.61 eV was obtained for all investigated samples from fitting the extrapolations of the Urbach tails. Burstein-Moss effect, electron-impurity, and electron-electron interactions are shown to play a minor role for the shift of the absorption edges in SnO2:N thin films.

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

    PubMed Central

    Derricotte, Wallace D.; Evangelista, Francesco A.

    2015-01-01

    Orthogonality constrained density functional theory (OCDFT) 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. PMID:25690350

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

    PubMed

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

    2013-08-26

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

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

    NASA Technical Reports Server (NTRS)

    Moisan, John R.; Moisan, Tiffany A. H.; Linkswiler, Matthew A.

    2011-01-01

    Phytoplankton absorption spectra and High-Performance Liquid Chromatography (HPLC) pigment observations from the Eastern U.S. and global observations from NASA's SeaBASS archive are used in a linear inverse calculation to extract pigment-specific absorption spectra. Using these pigment-specific absorption spectra to reconstruct the phytoplankton absorption spectra results in high correlations at all visible wavelengths (r(sup 2) from 0.83 to 0.98), and linear regressions (slopes ranging from 0.8 to 1.1). Higher correlations (r(sup 2) from 0.75 to 1.00) are obtained in the visible portion of the spectra when the total phytoplankton absorption spectra are unpackaged by multiplying the entire spectra by a factor that sets the total absorption at 675 nm to that expected from absorption spectra reconstruction using measured pigment concentrations and laboratory-derived pigment-specific absorption spectra. The derived pigment-specific absorption spectra were further used with the total phytoplankton absorption spectra in a second linear inverse calculation to estimate the various phytoplankton HPLC pigments. A comparison between the estimated and measured pigment concentrations for the 18 pigment fields showed good correlations (r(sup 2) greater than 0.5) for 7 pigments and very good correlations (r(sup 2) greater than 0.7) for chlorophyll a and fucoxanthin. Higher correlations result when the analysis is carried out at more local geographic scales. The ability to estimate phytoplankton pigments using pigment-specific absorption spectra is critical for using hyperspectral inverse models to retrieve phytoplankton pigment concentrations and other Inherent Optical Properties (IOPs) from passive remote sensing observations.

  12. Obtaining X-ray absorption near-edge structure for transition metal oxides via the Bethe-Salpeter equation

    NASA Astrophysics Data System (ADS)

    Liang, Yufeng; Vinson, John; Pemmaraju, Sri; Shirley, Eric; Prendergast, David

    Transition metal oxides are an important class of materials featured with strongly correlated effects. Most interesting and yet to-be-unveiled physics is associated with the metal 3d orbitals, which can be probed by X-ray absorption near-edge spectroscopy. A thorough interpretation of the x-ray spectroscopy is often accompanied with first-principles simulations of structures, electronic properties and the corresponding x-ray spectra. However, the simulation for TMOs is particularly challenging with the localized 3d orbitals. Most previous studies relied on the ground-state calculations without the core-hole as a compromise. Other treated the excited atom as a charged impurity but the calculated spectra turn out to be even more deviated from experiments. Here, we present the first study for the O K-edge for several typical TMOs via solving the Bethe-Salpeter equation (BSE). We have found that electron-core-hole interactions can alter the absorption spectra significantly. Our study helps to disentangle core-hole effects from the intrinsic electron correlations and hence facilitates the development of more advanced many-electron theories.

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

    SciTech Connect

    Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye; Jurss, Jonah W.; Concepcion, Javier J.; Meyer, Thomas J.; Soldatov, Alexander; Pushkar, Yulia

    2015-09-17

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

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

    DOE PAGES

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

    2016-06-30

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

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

    PubMed

    Timoshenko, Janis; Shivhare, Atal; Scott, Robert W J; Lu, Deyu; Frenkel, Anatoly I

    2016-07-20

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

  16. Calculation of near-edge x-ray-absorption fine structure at finite temperatures: spectral signatures of hydrogen bond breaking in liquid water.

    PubMed

    Hetényi, Balázs; De Angelis, Filippo; Giannozzi, Paolo; Car, Roberto

    2004-05-08

    We calculate the near-edge x-ray-absorption fine structure of H(2)O in the gas, hexagonal ice, and liquid phases using heuristic density-functional based methods. We present a detailed comparison of our results with experiment. The differences between the ice and water spectra can be rationalized in terms of the breaking of hydrogen bonds around the absorbing molecule. In particular the increase in the pre-edge absorption feature from ice to water is shown to be due to the breaking of a donor hydrogen bond. We also find that in water approximately 19% of hydrogen bonds are broken.

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

    NASA Astrophysics Data System (ADS)

    Terada, Hiroshi; Tokunaga, Alan T.

    2017-01-01

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

  18. Direct Determination of Oxidation States of Uranium in Mixed-Valent Uranium Oxides Using Total Reflection X-ray Fluorescence X-ray Absorption Near-Edge Spectroscopy.

    PubMed

    Sanyal, Kaushik; Khooha, Ajay; Das, Gangadhar; Tiwari, M K; Misra, N L

    2017-01-03

    Total reflection X-ray fluorescence (TXRF)-based X-ray absorption near-edge spectroscopy has been used to determine the oxidation state of uranium in mixed-valent U3O8 and U3O7 uranium oxides. The TXRF spectra of the compounds were measured using variable X-ray energies in the vicinity of the U L3 edge in the TXRF excitation mode at the microfocus beamline of the Indus-2 synchrotron facility. The TXRF-based X-ray absorption near-edge spectroscopy (TXRF-XANES) spectra were deduced from the emission spectra measured using the energies below and above the U L3 edge in the XANES region. The data processing using TXRF-XANES spectra of U(IV), U(V), and U(VI) standard compounds revealed that U present in U3O8 is a mixture of U(V) and U(VI), whereas U in U3O7 is mixture of U(IV) and U(VI). The results obtained in this study are similar to that reported in literature using the U M edge. The present study has demonstrated the possibility of application of TXRF for the oxidation state determination and elemental speciation of radioactive substances in a nondestructive manner with very small amount of sample requirement.

  19. Multiple-scattering calculations of the uranium {ital L}{sub 3}-edge x-ray-absorption near-edge structure

    SciTech Connect

    Hudson, E.A.; Rehr, J.J.; Bucher, J.J.

    1995-11-15

    A theoretical study of the uranium {ital L}{sub 3}-edge x-ray absorption near-edge structure (XANES) is presented for several uranium compounds, including oxides, intermetallics, uranyl fluoride, and {alpha}-uranium. Calculations were performed using FEFF6, an {ital ab} {ital initio} multiple-scattering (MS) code that includes the most important features of current theories. The results, which account for both the fine structure {chi} and the atomiclike background {mu}{sub 0} of the absorption coefficient {mu}, are compared to new and previously measured experimental spectra, reavealing very good agreement for most systems. For several compounds, a more detailed theoretical analysis determined the influence of cluster size and scattering order upon the calculated spectra. Results indicate that MS paths and scattering paths that include rather distant atoms make significant contributions for UO{sub 2}, whereas XANES for crystals with lower symmetry and density can be modeled using only shorter single-scattering paths. In most cases, assumption of a screened final state in the calculation gives better agreement with experiment than use of an unscreened final state. The successful modeling of spectra for a variety of different uranium compounds, with differing spectral features, indicates that the semirelativistic treatment of XANES used here is adequate even for heavy elements. The well-known resonance, observed experimentally for uranyl (UO{sub 2}{sup 2+}) compounds {approx}15 eV above the white line, is successfully modeled here for the first time, using multiple-scattering paths within the O-U-O axial bonds. Overlapping muffin-tin spheres were required in the calculation, probably as a result of the short uranyl axial bonds.

  20. [Decomposition of hemoglobin UV absorption spectrum into absorption spectra of prosthetic group and apoprotein by means of an additive model].

    PubMed

    Lavrinenko, I A; Vashanov, G A; Artyukhov, V G

    2015-01-01

    The decomposition pathways of hemoglobin UV absorption spectrum into the absorption spectra of the protein and non-protein components are proposed and substantiated by means of an additive model. We have established that the heme component has an absorption band with a maximum at λ(max) = 269.2 nm (ε = 97163) and the apoprotein component has an absorption band with a maximum at λ(max) = 278.4 nm (ε = 48669) for the wavelength range from 240.0 to 320.0 nm. An integral relative proportion of absorption for the heme fraction (78.8%) and apoprotein (21.2%) in the investigating wavelength range is defined.

  1. [Absorption spectra of nucleic acids and related compounds in the spectral region 120--280 nm].

    PubMed

    Kiseleva, M N; Zarochentseva, E P; Dodonova, N Ia

    1975-01-01

    The absorption spectra of thin films of nucleic acids, nucleosides, nucleotides, D-ribose, Na3PO4 in vacuum ultraviolet region are measured. In the spectral region 280--160 nm the absorption spectra consist of the bands of nucleic acid bases. In the range shorter than 160 nm the absorption is determined by phosphate and D-ribose groups. The methods of thin films preparation are discussed.

  2. A QM/MM study of absorption spectra of uracil derivatives in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nakayama, Akira

    2016-12-01

    The absorption spectra of three representative uracil derivatives (uracil, thymine, and 5-fluorouracil) in aqueous solution are investigated by the QM/MM approach, where the CASPT2 method is employed to evaluate the excitation energies. The computed absorption spectra are in good agreement with the experimental results, and in particular, the relative values of the absorption maximum between these derivatives are well reproduced in the simulations.

  3. Progress in the Theory and Interpretation of X-ray Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Rehr, J. J.

    2002-03-01

    There has been dramatic progress in recent years in the understanding of x-ray absorption spectra (XAS) [1]. For example, modern real space multiple scattering theory has yielded a quantitative treatment of the extended fine structure in XAS. Crucial in the theory is a treatment of electronic excited states including many-body effects such as inelastic losses and Debye-Waller factors. These developments have led to ab initio codes which permit an interpretation of the spectra in terms of geometrical and electronic properties of materials [2]. Indeed, the availability of such codes has revolutionized experimental investigations based on synchrotron radiation x-ray sources. Algorithmic improvements have recently made possible fast, parallel calculations of the near edge structure (XANES) [3], and approximate treatments of local field effects and many-body amplitude factors. Related techniques have been applied to several other spectroscopies, e.g., anomalous x-ray scattering, x-ray magnetic circular dichroism, and photoelectron diffraction [4]. [1] J. J. Rehr and R. C. Albers, Rev. Mod. Phys. 72, 621 (2000); [2] A. L. Ankudinov, B. Ravel, J.J. Rehr, and S. Conradson, Phys. Rev. B 58, 7565 (1998); [3] A. L. Ankudinov, C. E. Bouldin, J. J. Rehr, J. Sims, and H. Hung, Phys. Rev. B, in press (2002); [4] F. J. Garcia de Abajo, M. A. Van Hove, C. S. Fadley, Phys. Rev. B 63, 075404 (2001).

  4. X-ray Absorption Spectra of Dissolved Polysulfides in Lithium-Sulfur Batteries from First-Principles.

    PubMed

    Pascal, Tod A; Wujcik, Kevin H; Velasco-Velez, Juan; Wu, Chenghao; Teran, Alexander A; Kapilashrami, Mukes; Cabana, Jordi; Guo, Jinghua; Salmeron, Miquel; Balsara, Nitash; Prendergast, David

    2014-05-01

    The X-ray absorption spectra (XAS) of lithium polysulfides (Li2Sx) of various chain lengths (x) dissolved in a model solvent are obtained from first-principles calculations. The spectra exhibit two main absorption features near the sulfur K-edge, which are unambiguously interpreted as a pre-edge near 2471 eV due to the terminal sulfur atoms at either end of the linear polysulfide dianions and a main-edge near 2473 eV due to the (x - 2) internal atoms in the chain, except in the case of Li2S2, which only has a low-energy feature. We find an almost linear dependence between the ratio of the peaks and chain length, although the linear dependence is modified by the delocalized, molecular nature of the core-excited states that can span up to six neighboring sulfur atoms. Thus, our results indicate that the ratio of the peak area, and not the peak intensities, should be used when attempting to differentiate the polysulfides from XAS.

  5. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

    PubMed

    Schreck, Simon; Wernet, Philippe

    2016-09-14

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

  6. Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge

    NASA Astrophysics Data System (ADS)

    Schreck, Simon; Wernet, Philippe

    2016-09-01

    The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

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

    PubMed

    Vasseur, Romain; Moore, Joel E

    2014-04-11

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

  8. On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre.

    PubMed

    Bergmann, Nora; Bonhommeau, Sébastien; Lange, Kathrin M; Greil, Stefanie M; Eisebitt, Stefan; de Groot, Frank; Chergui, Majed; Aziz, Emad F

    2010-05-14

    Catalase and methaemoglobin have very similar haem groups, which are both ferric, yet catalase decomposes hydrogen peroxide to water and oxygen very efficiently, while methaemoglobin does not. Structural studies have attributed this behaviour to their different distal environments. Here we present Fe L(2,3)-edge X-ray absorption spectra of these proteins in physiological solutions, which reveal clear differences in their electronic structures, in that pi back-donation of the Fe atom occurs in catalase, which confers on it a partial ferryl (Fe(4+)) character, while this is not the case in methaemoglobin. The origin of the Fe(4+) character stems from the proximal tyrosine residue. We also find that both systems are in a high spin state. Temperature effects influence the spectra of catalase only weakly, in agreement with previous studies of its chemical activity. We conclude that the high activity of catalase is not only determined by its distal environment but also by its partial ferryl character.

  9. Molecular dynamics and reverse Monte Carlo modeling of scheelite-type AWO4 (A = Ca, Sr, Ba) W L 3-edge EXAFS spectra

    NASA Astrophysics Data System (ADS)

    Kalinko, Aleksandr; Bauer, Matthias; Timoshenko, Janis; Kuzmin, Alexei

    2016-11-01

    Classical molecular dynamics (MD) and reverse Monte Carlo methods coupled with ab initio multiple-scattering extended x-ray absorption fine structure (EXAFS) calculations were used for modeling of scheelite-type AWO4 (A = Ca, Sr, Ba) W L 3-edge EXAFS spectra. The two theoretical approaches are complementary and allowed us to perform analysis of full EXAFS spectra. Both methods reproduce well the structure and dynamics of tungstates in the outer coordination shells, however the classical MD simulations underestimate the W-O bond MSRD due to a neglect of quantum zero-point-motion. The thermal vibration amplitudes, correlation effects and anisotropy of the tungstate structure were also estimated.

  10. Near edge X-ray absorption mass spectrometry on coronene

    SciTech Connect

    Reitsma, G.; Deuzeman, M. J.; Hoekstra, R.; Schlathölter, T.; Boschman, L.; Hoekstra, S.

    2015-01-14

    We have investigated the photoionization and photodissociation of free coronene cations C{sub 24}H{sub 12}{sup +} upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C{sub 24}H{sub 12}{sup 3+⋆}trications, the experimental data hint at loss of H{sup +} ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

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

    PubMed

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  12. Near-edge x-ray absorption fine structure measurements using a laboratory-scale XUV source

    NASA Astrophysics Data System (ADS)

    Peth, Christian; Barkusky, Frank; Mann, Klaus

    2008-05-01

    We present a compact setup for near-edge x-ray absorption spectroscopy at the carbon K-edge based on a laser-driven plasma source. To generate the required broad-band emission in the spectral range of the 'water window' (λ = 2.2-4.4 nm) a krypton gas puff target was used. The table-top setup consisting basically of the laser-plasma source and a flat-field spectrometer can be used for near-edge x-ray absorption fine structure experiments in transmission as well as reflection under grazing incidence conditions (ReflEXAFS). The latter method offers the advantage that thin film preparation is not necessary and that the surface sensitivity is strongly enhanced. The results obtained for thin polymer films show good agreement with synchrotron data. Furthermore, we use the ReflEXAFS method to investigate changes in the chemical composition of PMMA induced by extreme ultraviolet (EUV) radiation. The spectra indicate a loss of the carbonyl functional group upon irradiation as well as crosslinking effects at high EUV radiation doses.

  13. Local disorder investigation in NiS(2-x)Se(x) using Raman and Ni K-edge x-ray absorption spectroscopies.

    PubMed

    Marini, C; Joseph, B; Caramazza, S; Capitani, F; Bendele, M; Mitrano, M; Chermisi, D; Mangialardo, S; Pal, B; Goyal, M; Iadecola, A; Mathon, O; Pascarelli, S; Sarma, D D; Postorino, P

    2014-11-12

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS(2-x)Se(x) Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS(2-x)Se(x) pyrites.

  14. Use of L-edge X-ray absorption spectroscopy to characterize multiple valence states of 3 d transition metals; a new probe for mineralogical and geochemical research

    NASA Astrophysics Data System (ADS)

    Cressey, G.; Henderson, C. M. B.; van der Laan, G.

    1993-07-01

    2 p ( L 2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2 p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3 d n → 2 p 5 3 d n+1 transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu3 VS4) indicates the presence of both Cu+ and Cu2+; the V L-edge spectrum of the same sample shows that both V2+ and V5+ are present. Spectral simulations representing mixtures of Fe d 5 and Fe d 6 states are used to quantify Fe3+/ ∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2 p XAS in a dilute system, the Fe L-edge spectrum of amethyst ( α-SiO2: Fe) has been recorded; this spectrum shows that ˜68% of the Fe in amethyst is Fe2+, and ˜32% is Fe3+. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe4+, there is no indication in the L-edge spectrum for Fe4+ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.

  15. Influence of substitution on the T-T absorption spectra in furocoumarins

    NASA Astrophysics Data System (ADS)

    Bryantseva, N. G.

    2006-11-01

    The present paper deals with compounds called photosensitizers, namely, psoralen, 3,4-phenyl-4',5'- cyclohexylpsoralen, 4'-methyl-3,4-cycloheptyl psoralen, 4',5'-dimethyl-3,4-cyclohexyl psoralen (fig. 1). The absorption spectra from excited triplets states were investigated. The computed triplet-triplet absorption spectra of research compounds have been determined using INDO method. The experimental triplet-triplet absorption spectra have been obtained using the technique of laser flash photolysis in ethanol. The compare of computed and experimental data is shows that the computed second band wavelenght throughout agree very well (0,5-6 nm) with experimental data.

  16. [Terahertz Absorption Spectra Simulation of Glutamine Based on Quantum-Chemical Calculation].

    PubMed

    Zhang, Tian-yao; Zhang, Zhao-hui; Zhao, Xiao-yan; Zhang, Han; Yan, Fang; Qian, Ping

    2015-08-01

    With simulation of absorption spectra in THz region based on quantum-chemical calculation, the THz absorption features of target materials can be assigned with theoretical normal vibration modes. This is necessary for deeply understanding the origin of THz absorption spectra. The reliabilities of simulation results mainly depend on the initial structures and theoretical methods used throughout the calculation. In our study, we utilized THz-TDS to obtain the THz absorption spectrum of solid-state L-glutamine. Then three quantum-chemical calculation schemes with different initial structures commonly used in previous studies were proposed to study the inter-molecular interactions' contribution to the THz absorption of glutamine, containing monomer structure, dimer structure and crystal unit cell structure. After structure optimization and vibration modes' calculation based on density functional theory, the calculation results were converted to absorption spectra by Lorentzian line shape function for visual comparison with experimental spectra. The result of dimmer structure is better than monomer structure in number of absorption features while worse than crystal unit cell structure in position of absorption peaks. With the most reliable simulation result from crystal unit cell calculation, we successfully assigned all three experimental absorption peaks of glutamine ranged from 0.3 to 2.6 THz with overall vibration modes. Our study reveals that the crystal unit cell should be used as initial structure during theoretical simulation of solid-state samples' THz absorption spectrum which comprehensively considers not only the intra-molecular interactions but also inter-molecular interactions.

  17. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  18. Luminescence and Absorption Spectra of C sub 60 Films

    DTIC Science & Technology

    1991-02-01

    which contains 60 atoms lying at the vertices of a truncated icosahedron, is known as Buckminsterfullerene because the geodesic structures of Buckminster ... Fuller led to the initial proposal of its structure.9 Solutions of C60 are magenta; the long wavelength ahr ction edge lies at about 620 rnm.3 It n

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

    PubMed

    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.

  20. Systematic view of optical absorption spectra in the actinide series

    SciTech Connect

    Carnall, W.T.

    1985-01-01

    In recent years sufficient new spectra of actinides in their numerous valence states have been measured to encourage a broader scale analysis effort than was attempted in the past. Theoretical modelling in terms of effective operators has also undergone development. Well established electronic structure parameters for the trivalent actinides are being used as a basis for estimating parameters in other valence states and relationships to atomic spectra are being extended. Recent contributions to our understanding of the spectra of 4+ actinides have been particularly revealing and supportive of a developing general effort to progress beyond a preoccupation with modelling structure to consideration of the much broader area of structure-bonding relationships. We summarize here both the developments in modelling electronic structure and the interpretation of apparent trends in bonding. 60 refs., 9 figs., 1 tab.

  1. Applications of principal component analysis to breath air absorption spectra profiles classification

    NASA Astrophysics Data System (ADS)

    Kistenev, Yu. V.; Shapovalov, A. V.; Borisov, A. V.; Vrazhnov, D. A.; Nikolaev, V. V.; Nikiforova, O. Y.

    2015-12-01

    The results of numerical simulation of application principal component analysis to absorption spectra of breath air of patients with pulmonary diseases are presented. Various methods of experimental data preprocessing are analyzed.

  2. Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

    NASA Technical Reports Server (NTRS)

    Hoepffner, Nicolas; Sathyendranath, Shubha

    1993-01-01

    The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

  3. Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

    NASA Astrophysics Data System (ADS)

    Hoepffner, Nicolas; Sathyendranath, Shubha

    1993-12-01

    The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

  4. Vibronic fine structure in high-resolution x-ray absorption spectra from ion-bombarded boron nitride nanotubes

    SciTech Connect

    Petravic, Mladen; Peter, Robert; Varasanec, Marijana; Li Luhua; Chen Ying; Cowie, Bruce C. C.

    2013-05-15

    The authors have applied high-resolution near-edge x-ray absorption fine structure measurements around the nitrogen K-edge to study the effects of ion-bombardment on near-surface properties of boron nitride nanotubes. A notable difference has been observed between surface sensitive partial electron yield (PEY) and bulk sensitive total electron yield (TEY) fine-structure measurements. The authors assign the PEY fine structure to the coupling of excited molecular vibrational modes to electronic transitions in NO molecules trapped just below the surface. Oxidation resistance of the boron nitride nanotubes is significantly reduced by low energy ion bombardment, as broken B-N bonds are replaced by N-O bonds involving oxygen present in the surface region. In contrast to the PEY spectra, the bulk sensitive TEY measurements on as-grown samples do not exhibit any fine structure while the ion-bombarded samples show a clear vibronic signature of molecular nitrogen.

  5. Searching for narrow absorption and emission lines in XMM-Newton spectra of gamma-ray bursts

    NASA Astrophysics Data System (ADS)

    Campana, S.; Braito, V.; D'Avanzo, P.; Ghirlanda, G.; Melandri, A.; Pescalli, A.; Salafia, O. S.; Salvaterra, R.; Tagliaferri, G.; Vergani, S. D.

    2016-08-01

    We present the results of a spectroscopic search for narrow emission and absorption features in the X-ray spectra of long gamma-ray burst (GRB) afterglows. Using XMM-Newton data, both EPIC and RGS spectra, of six bright (fluence > 10-7 erg cm-2) and relatively nearby (z = 0.54-1.41) GRBs, we performed a blind search for emission or absorption lines that could be related to a high cloud density or metal-rich gas in the environ close to the GRBs. We detected five emission features in four of the six GRBs with an overall statistical significance, assessed through Monte Carlo simulations, of ≲ 3.0σ. Most of the lines are detected around the observed energy of the oxygen edge at ~ 0.5 keV, suggesting that they are not related to the GRB environment but are most likely of Galactic origin. No significant absorption features were detected. A spectral fitting with a free Galactic column density (NH) testing different models for the Galactic absorption confirms this origin because we found an indication of an excess of Galactic NH in these four GRBs with respect to the tabulated values.

  6. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H.; Holroyd, R.A.; Yang, B.X.

    1992-12-31

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH{sub 3}){sub 4},Si [(CH{sub 3}){sub 3}Si]{sub 4}Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl{sub 4} at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl{sub 4} is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  7. Photoconductivity measurements of x-ray absorption fine structures in liquids in the soft x-ray region: Si and Cl K-edge

    SciTech Connect

    Sham, T.K.; Xiong, J.Z.; Feng, X.H. . Dept. of Chemistry); Holroyd, R.A. ); Yang, B.X. )

    1992-01-01

    Photoconductivity measurements of X-ray absorption fine structures (XAFS) at the Si and Cl K-edge have been carried out in a liquid cell for (CH[sub 3])[sub 4],Si [(CH[sub 3])[sub 3]Si][sub 4]Si and eitheras a pure liquid or 2,2,4-trimethylpentane solution. It is found that for the pure liquids and their concentrated hydrocarbon solutions, all K-edge XAFS spectra are inverted as expected under the condition of total absorption. A sharp conductivity dip is also observed in CCl[sub 4] at the Cl K-edge. The concentration dependence of the XAFS spectrum of CCl[sub 4] is reported. These results are discussed in terms of soft X-ray induced ion yields of the solute and solvent molecules in liquids.

  8. Theory of edge-state optical absorption in two-dimensional transition metal dichalcogenide flakes

    NASA Astrophysics Data System (ADS)

    Trushin, Maxim; Kelleher, Edmund J. R.; Hasan, Tawfique

    2016-10-01

    We develop an analytical model to describe sub-band-gap optical absorption in two-dimensional semiconducting transition metal dichalcogenide (s-TMD) nanoflakes. The material system represents an array of few-layer molybdenum disulfide crystals, randomly orientated in a polymer matrix. We propose that optical absorption involves direct transitions between electronic edge states and bulk bands, depends strongly on the carrier population, and is saturable with sufficient fluence. For excitation energies above half the band gap, the excess energy is absorbed by the edge-state electrons, elevating their effective temperature. Our analytical expressions for the linear and nonlinear absorption could prove useful tools in the design of practical photonic devices based on s-TMDs.

  9. Electronic absorption spectra of blood plasma of patients with various forms of goiter

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    The results of absorption spectra of blood plasma in the ultraviolet and visible areas of the spectrum using the technique of spherical photometer. Possibilities of using these spectra to detect the diseases - diffuse toxic goiter and nodular euthyroid goiter and to control the surgical treatment of this pathology.

  10. Electronic absorption spectra of blood plasma of patients with various forms of goiter

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

    The results of absorption spectra of blood plasma in the ultraviolet and visible areas of the spectrum using the technique of spherical photometer. Possibilities of using these spectra to detect the diseases - diffuse toxic goiter and nodular euthyroid goiter and to control the surgical treatment of this pathology.

  11. Analysis of absorption and scattering spectra for assessing apple fruit internal quality after harvest and storage

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Optical absorption and scattering properties are useful for quantifying light interaction with plant tissue, as well as for quality assessment of horticultural products. The aim of this research was to measure the absorption and reduced scattering coefficient spectra of two cultivars of apple (Malus...

  12. The absorption spectra of the complexes of uranium (VI) with some β-diketones

    USGS Publications Warehouse

    Feinstein, H.I.

    1956-01-01

    The absorption spectra of the complexes of uranium (VI) with four β-dike tones were determined under various conditions of pH, concentration of uranium, and alcohol concentration. Under optimum conditions, the maximum molar absorptivity (31,200) is obtained using 2-furoyltrifluoroacetone. This compares with about 4,000 and 19,000 for the thiocyanate and dibenzoylmethane complexes, respectively.

  13. NOTE: Near surface photon energy spectra outside a 6 MV field edge

    NASA Astrophysics Data System (ADS)

    Edwards, C. R.; Mountford, P. J.

    2004-09-01

    The purpose of this study was to investigate the difference between a 6 MV linear accelerator x-ray energy spectrum outside the field edge near a phantom surface, and the corresponding spectrum on the central axis. The Monte Carlo code MCNP-4A was used to calculate the spectra on the central axis and at 1, 2, 5 and 10 cm from the edge of a 4 × 4 cm2, 10 × 10 cm2 and 15 × 15 cm2 field. Compared to the spectrum on the central axis, the spectra outside the field edge showed two distinct regions: a broad peak below about 0.5 MeV, and a lower amplitude, less rapidly changing region at higher energies from 0.5 to 6 MeV. The lower energy peak was due to scattered photons, and the higher energy component was due mainly to primary photons transmitted through the jaws of the secondary collimator. The potential impact of these spectral differences on critical organ photon dosimetry was determined by calculating the ratio of the sensitivity of a Scanditronix EDD-5 diode and of a LiF:Mg:Ti thermoluminescent dosimeter (TLD) outside the field edge to their respective sensitivity at the calibration position on the central axis. The lower energy peak combined with the non-uniform energy sensitivity of each detector produced up to a two-thirds overestimate of x-ray dose outside the field by the diode, whereas the response ratio of the TLD was about unity. These results indicated that a similar evaluation was required for profile measurements of a dynamic wedged field and measurements in an intensity modulated beam with either type of detector.

  14. The Extragalactic Background Light and Absorption in Gamma Ray Spectra

    NASA Astrophysics Data System (ADS)

    Gilmore, Rudy C.

    2008-03-01

    Recent state-of-the-art semi-analytic models (SAMs) can now accurately model the history of galaxy formation and evolution. These SAMs utilize a 'forward evolution' approach and include all of the important processes for determining photon emission from galaxies, such as cooling and shock heating of gas, galaxy mergers, star formation and aging, supernova and AGN feedback, and the reprocessing of light by dust. I will be presenting our group's latest prediction of the extra-galactic background light based on this work and will discuss the implications for the attenuation of VHE gamma rays from distant sources due to pair-production. These results will be compared to recent limits placed on the EBL by observations of GeV and TeV blazar spectra by experiments such as H.E.S.S., MAGIC and VERITAS. The implications for reconstructing the intrinsic spectra of distant blazars will be addressed.

  15. On the nitrogen-induced far-infrared absorption spectra

    NASA Technical Reports Server (NTRS)

    Dore, P.; Filabozzi, A.

    1987-01-01

    The rototranslational absorption spectrum of gaseous N2 is analyzed, considering quadrupolar and hexadecapolar induction mechanisms. The available experimental data are accounted for by using a line-shape analysis in which empirical profiles describe the single-line translational profiles. Thus, a simple procedure is derived that allows the prediction of the N2 spectrum at any temperature. On the basis of the results obtained for the pure gas, a procedure to compute the far-infrared spectrum of the N2-Ar gaseous mixture is also proposed. The good agreement between computed and experimental N2-Ar data indicates that it is possible to predict the far-infrared absorption induced by N2 on the isotropic polarizability of any interacting partner.

  16. An iron absorption model of gamma-ray burst spectra

    NASA Technical Reports Server (NTRS)

    Liang, Edison P.; Kargatis, Vincent E.

    1994-01-01

    Most gamma-ray bursts (GRBs) exhibit deficits of X-rays below approximately 200 keV. Here we consider a spectral model in which the burst source is shielded by an optically thick layer of circumburster material (CBM) rich in iron-group elements whose photoelectric absorption opacity exceeds the Thomson opacity below approximately 120 keV. For power-law distributions of absorption depths along the lines of sight the absorbed spectrum can indeed mimic the typial GRB spectrum. This model predicts that (a) the spectrum should evolve monotonically from hard to soft during each energy release, which is observed in most bursts, especially in fast rise exponential decay bursts; (b) Fe spectral features near 7 keV may be present in some bursts; and (c) the ratio of burst distances to the CBM and to Earth should be approximately 10(exp -11) if the spectral evolution is purely due to Fe stripping by the photons.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

    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.

  19. Absorption Spectra of High-Temperature Solid Propellant Flames

    DTIC Science & Technology

    1974-08-01

    emission, was used as the calibration parameter. A Beer -Lambert type plot of the modified absorbance versus the respective specie concentration...the flame. Where P°^ is the incident radiant power at wave- length X, and P^ is the transmitted radiant power at wavelength A. Beer -Lambert type...absorption spectroscopy is based on the use of the Beer -Lambert Law, 103 P? ^n-^-»Kxce , (1) where P*J is the Incident radiant power, P^ is the

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

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2014-03-01

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

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

    PubMed

    Derricotte, Wallace D; Evangelista, Francesco A

    2015-06-14

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

  2. Ab-initio method for X-ray absorption spectra simulation of hydride molecular ions

    NASA Astrophysics Data System (ADS)

    Puglisi, Alessandra; Sisourat, Nicolas; Carniato, Stéphane

    2017-03-01

    Soft X-ray absorption spectra of molecular ions are important data for the modeling and understanding of laboratory and astrophysical plasma. In this work, we present an ab-initio method, based on the Configuration Interaction (CI) approach, for the calculations of energy positions and oscillator strengths of X-ray absorption spectra. Furthermore, we investigate the effects of the choice of the nature and number of spin-orbitals used in the CI expansion on the spectra. The method is applied on three hydride molecular ions, namely CH+, OH+ and SiH+. However, the approach proposed here is general and may thus be applied to any kind of molecular ions.

  3. X-ray absorption near-edge structure of selenium in the Cu-In-Se system

    NASA Astrophysics Data System (ADS)

    Wolska, A.; Bacewicz, R.; Filipowicz, J.; Attenkofer, K.

    2001-05-01

    The x-ray absorption near edge structure (XANES) of selenium is investigated in the crystals with compositions from the pseudobinary cut line Cu2Se-In2Se3. This includes CuInSe2, indium-rich ternary compounds (Cu2In4Se7, CuIn3Se5, CuIn5Se8, CuIn7Se11) and α-In2Se3. The absorption at the K and L3/L2 edges of selenium has been measured using synchrotron radiation. Two theoretical approaches are used to the interpretation of the experimental data: the band structure calculation and the real-space multiple-scattering (RSMS) method. In the first one, the angular momentum projected densities of states at Se sites are calculated for CuInSe2 and α-In2Se3 for the energies up to 17 eV above the conduction band minimum by the LMTO-ASA method. The RSMS approach represented by the FEFF8 code is used to calculate the XANES spectra for the phases with tetragonal symmetry. Clusters up to 160 atoms are used in the calculations. The influence of different structural factors on the selenium XANES is studied.

  4. Electronic structure and TDDFT optical absorption spectra of silver nanorods.

    PubMed

    Johnson, Hannah E; Aikens, Christine M

    2009-04-23

    Density functional theory calculations are employed to determine optimized geometries and excitation spectra for small pentagonal silver nanorods Ag(n), with n = 13, 19, 25, 31, 37, 43, 49, 55, 61, and 67 in various charge states. The asymptotically correct SAOP functional is utilized in the excitation calculations. Silver nanorods exhibit a sharp longitudinal excitation that results from a mixture of orbital transitions; the wavelength for this excitation depends linearly on the length of the nanorod. The broad transverse excitation arises from multiple excited states. A particle-in-a-box model is employed to explain the linear dependence of the longitudinal excitation wavelength on nanorod length.

  5. Carbon dioxide laser absorption spectra of toxic industrial compounds.

    PubMed

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

    1982-05-01

    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 interferences in the detection of toxic hydrazine-based rocket fuels by CO(2) laser spectroscopic techniques.

  6. Femtosecond Transient Absorption Spectra and Relaxation Dynamics of SWNT in SDS Micellar Solutions

    NASA Astrophysics Data System (ADS)

    Nadtochenko, V. A.; Lobach, A. S.; Gostev, F. E.; Tcherbinin, D. O.; Sobennikov, A.; Sarkisov, O. M.

    2005-09-01

    Transient absorption spectra and relaxation dynamics of excited SWNT were studied by femtosecond absorption spectroscopy as a function of: the energy of excitation quanta (ℏω = 2 eV, 2.5 eV, 4 eV); the density of the excitation energy; polarizations of the pump and probe pulses. The transient absorption spectra were monitored by white supercontinuum light pulse in the spectral region of ˜ 1.2 ÷ 3.6 eV. The induced transient absorption spectra of SWNT are considered as filling of the size-quantized energy bands with nonequilibrium carriers; renormalization of the one-dimensional energy bands at high density of the induced plasma; quantum confined Stark effect and screening of excitons. The anisotropic relaxation rate is observed.

  7. In vivo absorption spectra of the two stable states of the Euglena photoreceptor photocycle.

    PubMed

    Barsanti, Laura; Coltelli, Primo; Evangelista, Valtere; Passarelli, Vincenzo; Frassanito, Anna Maria; Vesentini, Nicoletta; Santoro, Fabrizio; Gualtieri, Paolo

    2009-01-01

    Euglena gracilis possesses a simple but sophisticated light detecting system, consisting of an eyespot formed by carotenoids globules and a photoreceptor. The photoreceptor of Euglena is characterized by optical bistability, with two stable states. In order to provide important and discriminating information on the series of structural changes that Euglena photoreceptive protein(s) undergoes inside the photoreceptor in response to light, we measured the in vivo absorption spectra of the two stable states A and B of photoreceptor photocycle. Data were collected using two different devices, i.e. a microspectrophotometer and a digital microscope. Our results show that the photocycle and the absorption spectra of the photoreceptor possess strong spectroscopic similarities with a rhodopsin-like protein. Moreover, the analysis of the absorption spectra of the two stable states of the photoreceptor and the absorption spectrum of the eyespot suggests an intriguing hypothesis for the orientation of microalgae toward light.

  8. Direct Correlation Between Aromatization of Kerogen in Organic Shales during Maturation and Its Visible Absorption Edge

    NASA Astrophysics Data System (ADS)

    Ferralis, N.; Liu, Y.; Pomerantz, A.; Grossman, J.

    2014-12-01

    The evolution of the electronic visible-range optical absorption edge of isolated kerogens type 1, 2 (from organic shales) and 3 is characterized by diffuse reflectance UV-Visible absorption spectroscopy. The functional form of the electronic absorption edge for all kerogens measured is in excellent agreement with the "Urbach tail" phenomenology. The Urbach decay width extracted from the exponential fit within the visible range is strongly correlated with the aliphatic/aromatic ratio in isolated kerogen, regardless of the kerogen type. The direct correlation is confirmed by density functional theory calculations on proxy ensemble models of kerogen. The correlation of the decay width with conventional maturity indicators such as vitrinite reflectance is found to be good within a particular kerogen type, but not consistent across different kerogen types. This is explained in terms of the evolution of the population of aromatic constituents in kerogen, which is instead directly measured through the Urbach decay. The optical absorption edge and the Urbach decay width are therefore presented as excellent candidates for the evaluation of thermal maturity in kerogen.

  9. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark

    2016-06-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and to the interstellar medium, with an emphasis on amorphous and crystalline ices below ~ 120 K. Our goal is to update and add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on three of the simplest and most abundant components of interstellar and solar-system ices: methane (CH4), carbon dioxide (CO2), and methanol (CH3OH). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 120 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  10. Electronic absorption spectra of hydrogenated protonated naphthalene and proflavine

    NASA Astrophysics Data System (ADS)

    Bonaca, A.; Bilalbegović, G.

    2011-09-01

    We study hydrogenated cations of two polycyclic hydrocarbon molecules as models of hydrogenated organic species that form in the interstellar medium. Optical spectra of the hydrogenated naphthalene cation Hn-C10H+8 for n= 1, 2 and 10, as well as the astrobiologically interesting hydrogenated proflavine cation Hn-C13H11N+3 for n= 1 and 14, are calculated. The pseudopotential time-dependent density functional theory is used. It is found that the fully hydrogenated proflavine cation H14-C13H11N+3 shows a broad spectrum in which the positions of individual lines are almost lost. The positions, shapes and intensities of lines change in hydronaphthalene and hydroproflavine cations, showing that hydrogen additions induce substantially different optical spectra in comparison with base polycyclic hydrocarbon cations. One calculated line in the visible spectrum of H10-C10H+8 and one in the visible spectrum of H-C13H11N+3 are close to the measured diffuse interstellar bands. We also present the positions of near-ultraviolet lines.

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

    SciTech Connect

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

    2014-09-01

    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{sup 3}-10{sup 5} cm{sup –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.

  12. An x-ray absorption near edge structure spectroscopy study of metal coordination in Co(II)-substituted Carcinus maenas hemocyanin.

    PubMed Central

    Della Longa, S; Bianconi, A; Palladino, L; Simonelli, B; Congiu Castellano, A; Borghi, E; Barteri, M; Beltramini, M; Rocco, G P; Salvato, B

    1993-01-01

    High-resolution x-ray absorption near edge structure spectroscopy was used to characterize the metal sites in three different cobalt-substituted derivatives of Carcinus maenas hemocyanin (Hc), including a mononuclear cobalt, a dinuclear cobalt and a copper-cobalt hybrid derivative. Co(II) model complexes with structures exemplifying octahedral, trigonal bipyramidal, pseudo-tetrahedral, and square planar geometries were also studied. The results provide structural information about the metal binding site(s) in the Co-Hcs that extend earlier results from EPR and optical spectroscopy (Bubacco et al. 1992. Biochemistry. 31: 9294-9303). Experimental spectra were compared to those calculated for atomic clusters of idealized geometry, generated using a multiple scattering approach. The energy of the dipole forbidden 1s-->3d transition and of the absorption edge in the spectra for all cobalt Hc derivatives confirmed the cobaltous oxidation state which rules out the presence of an oxygenated site. Comparisons between data and simulations showed that the mononuclear and dinuclear Co(II) derivatives, as well as the hybrid derivative, contain four-coordinate Co(II) in distorted tetrahedral sites. Although the spectra for Co(II) in dinuclear metal sites more closely resemble the simulated spectrum for a tetrahedral complex than do spectra for the mononuclear derivative, the Co(II) sites in all derivatives are very similar. The Cu K-edge high resolution x-ray absorption near edge structure spectrum of the hybrid Cu-Co-Hc resembles that of deoxy-Hc demonstrating the presence of three-coordinate Cu(I). PMID:8312502

  13. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    NASA Astrophysics Data System (ADS)

    Dorchies, F.; Fedorov, N.; Lecherbourg, L.

    2015-07-01

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%-20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ˜1 mn and ˜100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

  14. X-ray absorption edge spectroscopy of Co(II)-binding sites of copper- and zinc-containing proteins.

    PubMed

    Desideri, A; Comin, F; Morpurgo, L; Cocco, D; Calabrese, L; Mondovi, B; Maret, W; Rotilio, G

    1981-10-28

    X-ray absorption near-edge spectroscopy (XANES) of Co(II) in three derivatives of superoxide dismutase, namely [Cu(II)-Co(II)], [Cu(I)-Co(II)] and [...-Co(II)], suggests a tetrahedral coordination of the metal for all compounds. Significant differences, detected in the spectrum of the [Cu(II)-Co(II)] derivative as compared to the other species, indicate that a conformational change and/or a different charge of the imidazole bridging the two metal sites in superoxide dismutase occur in coincidence with the change of copper valence. The XANES spectra of the cobalt derivatives of alcohol dehydrogenase, carbonic anhydrase and stellacyanin show features that can be accounted for by an increasing degree of covalency in the metal first sphere of coordination, in the following order: alcohol dehydrogenase greater than stellacyanin greater than superoxide dismutase greater than or equal to carbonic anhydrase.

  15. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N.

    2012-01-20

    Reduction-oxidation (redox) cycling of the nickel electrocatalyst phase in the solid oxide fuel cell (SOFC) anode can lead to performance degradation and cell failure. A greater understanding of nickel redox mechanisms at the microstructural level is vital to future SOFC development. Transmission x-ray microscopy (TXM) provides several key techniques for exploring oxidation states within SOFC electrode microstructure. Specifically, x-ray nanotomography and x-ray absorption near edge structure (XANES) spectroscopy have been applied to study samples of varying nickel (Ni) and nickel oxide (NiO) compositions. The imaged samples are treated as mock SOFC anodes containing distinct regions of the materials in question. XANES spectra presented for the individual materials provide a basis for the further processing and analysis of mixed samples. Images of composite samples obtained are segmented, and the distinct nickel and nickel oxide phases are uniquely identified using full field XANES spectroscopy. Applications to SOFC analysis are discussed.

  16. Electron-vibron coupling in halogenated acenaphthenequinone upon O K-edge soft x-ray absorption

    SciTech Connect

    Schmidt, Norman; Fink, Rainer H.; Clark, Tim; Urquhart, Stephen G.

    2011-10-14

    We present high resolution oxygen K near-edge x-ray absorption spectra of the acenaphthenequinone (ANQ) derivative 3,8-dibromo-5,6-dichloro-ANQ (Br{sub 2}Cl{sub 2}-ANQ). The spectral features exhibit an almost identical vibronic fine structure compared to that shown by ANQ. The unequal distances of the vibronic levels as derived from the least-squares fit analysis of the vibronic progressions allows us to determine the anharmonicity of the excited state potentials involved. We conclude that a single vibrational progression couples to the resonant excitation of O 1s core electrons preferentially. Comparison of the two ANQ derivatives gives a clear indication that the vibronic mode corresponds to a C=O stretching mode, rather than coupling to a C-H mode as suggested previously. These conclusions are supported by density functional theory calculations.

  17. Linewidths in excitonic absorption spectra of cuprous oxide

    NASA Astrophysics Data System (ADS)

    Schweiner, Frank; Main, Jörg; Wunner, Günter

    2016-02-01

    We present a theoretical calculation of the absorption spectrum of cuprous oxide (Cu2O ) based on the general theory developed by Y. Toyozawa. An inclusion not only of acoustic phonons but also of optical phonons and of specific properties of the excitons in Cu2O like the central-cell corrections for the 1 S exciton allows us to calculate the experimentally observed linewidths in experiments by T. Kazimierczuk et al. [T. Kazimierczuk, D. Fröhlich, S. Scheel, H. Stolz, and M. Bayer, Nature (London) 514, 343 (2014), 10.1038/nature13832] within the same order of magnitude, which demonstrates a clear improvement in comparison to earlier work on this topic. We also discuss a variety of further effects, which explain the still observable discrepancy between theory and experiment but can hardly be included in theoretical calculations.

  18. Absorption spectra of shocked liquid CS/sub 2/

    SciTech Connect

    Dallman, J.C.

    1985-01-01

    The importance of shock initiation of high explosives (HE) was understood as early as 1863 when Alfred Nobel introduced the detonator as a means of detonating nitroglycerine. The critical pressure rise times required to achieve shock initiation and steady propagation of detonation are determined by the chemical and mechanical properties of an explosive. Although progress has been made in the understanding of the effects of mechanical properties, the detailed effects of high pressures on chemical reaction mechanisms are still only poorly understood. This paper reports the results of two experiments using CS/sub 2/, which is known to undergo electronic state transitions when shocked to high pressures. The goal of these experiments was to examine the known shock-generated expansion of CS/sub 2/ absorption bands while generating the shocks with a flyer plate system driven by high explosives.

  19. Monitoring the Variability of Intrinsic Absorption Lines in Quasar Spectra

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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 ~103-105 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. Based on data collected at Subaru telescope, which is operated by the National Astronomical Observatory of Japan. Based on observations obtained at the European Southern Observatory at La Silla, Chile in programs 65.O-0063(B), 65.O-0474(A), 67.A-0078(A), 68.A-0461(A), 69.A-0204(A), 70.B-0522(A), 072.A-0346(A), 076.A-0860(A), 079.B-0469(A), and 166.A-0106(A).

  20. Simultaneous Fitting of Absorption Spectra and Their Second Derivatives for an Improved Analysis of Protein Infrared Spectra.

    PubMed

    Baldassarre, Maurizio; Li, Chenge; Eremina, Nadejda; Goormaghtigh, Erik; Barth, Andreas

    2015-07-10

    Infrared spectroscopy is a powerful tool in protein science due to its sensitivity to changes in secondary structure or conformation. In order to take advantage of the full power of infrared spectroscopy in structural studies of proteins, complex band contours, such as the amide I band, have to be decomposed into their main component bands, a process referred to as curve fitting. In this paper, we report on an improved curve fitting approach in which absorption spectra and second derivative spectra are fitted simultaneously. Our approach, which we name co-fitting, leads to a more reliable modelling of the experimental data because it uses more spectral information than the standard approach of fitting only the absorption spectrum. It also avoids that the fitting routine becomes trapped in local minima. We have tested the proposed approach using infrared absorption spectra of three mixed α/β proteins with different degrees of spectral overlap in the amide I region: ribonuclease A, pyruvate kinase, and aconitase.

  1. Intracellular nanoparticles mass quantification by near-edge absorption soft X-ray nanotomography

    PubMed Central

    Conesa, Jose Javier; Otón, Joaquín; Chiappi, Michele; Carazo, Jose María; Pereiro, Eva; Chichón, Francisco Javier; Carrascosa, José L.

    2016-01-01

    We used soft X-ray three-dimensional imaging to quantify the mass of superparamagnetic iron oxide nanoparticles (SPION) within whole cells, by exploiting the iron oxide differential absorption contrast. Near-edge absorption soft X-ray nanotomography (NEASXT) combines whole-cell 3D structure determination at 50 nm resolution, with 3D elemental mapping and high throughput. We detected three-dimensional distribution of SPIONs within cells with 0.3 g/cm3 sensitivity, sufficient for detecting the density corresponding to a single nanoparticle. PMID:26960695

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

    SciTech Connect

    Vittoria, Fabio A. Diemoz, Paul C.; Endrizzi, Marco; Olivo, Alessandro; Wagner, Ulrich H.; Rau, Christoph; Robinson, Ian K.

    2014-03-31

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

  3. Simultaneous acquisition of absorption and fluorescence spectra of strong absorbers utilizing an evanescent supercontinuum.

    PubMed

    Kiefer, Johannes

    2016-12-15

    The determination of the absorption and emission spectra of strongly absorbing molecules is challenging, and the data can be biased by self-absorption of the fluorescence signal. To overcome this problem, a total internal reflection approach is proposed. The strongly absorbing sample is placed in an evanescent field of the radiation of a supercontinuum source. The collimated reflected light encodes the absorption spectrum, and the isotropic fluorescence emission is collected in a direction perpendicular to the surface at the same time. This ensures that the emitted light has a minimum possibility of self-absorption inside the sample.

  4. Measurement and feature analysis of absorption spectra of four algal species

    NASA Astrophysics Data System (ADS)

    Zhu, Jianhua; Zhou, Hongli; Han, Bing; Li, Tongji

    2016-04-01

    Two methods for particulate pigments (i.e., quantitative filter technique, QFT, and in vivo measurement, InVivo, respectively) and two methods for dissolved pigments (i.e., Acetone Extracts, AceEx, and high-performance liquid chromatography, HPLC, respectively) were used to obtain the optical absorption coefficient spectra for cultures of four typical algal species. Through normalization and analysis of the spectra, it is shown that (1) the four methods are able to measure optical absorption spectra of particulate and/or dissolved pigments; (2) that the optical absorption spectra of particulate and dissolved pigments were consistent in terms of the peak position in the blue wavelength, and the difference of the peak position in the near infrared wavelength was ~10 nm between each other; and (3) that the leveling effect of the absorption spectra of particulate pigments was significant. These four methods can all effectively measure the absorption coefficients of phytoplankton pigments, while each one has its unique advantages in different applications. Therefore, appropriate method should be carefully selected for various application due to their intrinsic difference.

  5. Measurement and feature analysis of absorption spectra of four algal species

    NASA Astrophysics Data System (ADS)

    Zhu, Jianhua; Zhou, Hongli; Han, Bing; Li, Tongji

    2017-03-01

    Two methods for particulate pigments (i.e., quantitative filter technique, QFT, and in vivo measurement, InVivo, respectively) and two methods for dissolved pigments (i.e., Acetone Extracts, AceEx, and high-performance liquid chromatography, HPLC, respectively) were used to obtain the optical absorption coefficient spectra for cultures of four typical algal species. Through normalization and analysis of the spectra, it is shown that (1) the four methods are able to measure optical absorption spectra of particulate and/or dissolved pigments; (2) that the optical absorption spectra of particulate and dissolved pigments were consistent in terms of the peak position in the blue wavelength, and the difference of the peak position in the near infrared wavelength was 10 nm between each other; and (3) that the leveling effect of the absorption spectra of particulate pigments was significant. These four methods can all effectively measure the absorption coefficients of phytoplankton pigments, while each one has its unique advantages in different applications. Therefore, appropriate method should be carefully selected for various application due to their intrinsic difference.

  6. The effects of dust scattering on high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, L.; García, J.; Wilms, J.; Baganoff, F.

    2016-06-01

    High energy studies of astrophysical dust complement observations of dusty interstellar gas at other wavelengths. With high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. At soft energies, the spectrum of scattered light is likely to have significant features at the 0.3 keV (C-K), 0.5 keV (O-K), and 0.7 keV (Fe-L) photoelectric absorption edges. This direct probe of ISM dust grain elements will be important for (i) understanding the relative abundances of graphitic grains or PAHs versus silicates, and (ii) measuring the depletion of gas phase elements into solid form. We focus in particular on the Fe-L edge, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. We discuss ways in which spectroscopy with XMM can yield insight into dust obscured objects such as stars, binaries, AGN, and foreground quasar absorption line systems.

  7. Reassignment of the Iron (3) Absorption Bands in the Spectra of Mars

    NASA Technical Reports Server (NTRS)

    Sherman, D. M.

    1985-01-01

    Absorption features in the near-infrared and visible region reflectance spectra of Mars have been assigned to specific Fe (3+) crystal-field and o(2-) yields Fe(3+) charge transfer transitions. Recently, near-ultraviolet absorption spectra of iron oxides were obtained and the energies of o(2-) yields Fe(3+) charge-transfer (LMCT) transitions were determined from accurate SCF-X # alpha-SW molecular orbital calculations on (FeO6)(9-) and (FeO4)(5-) clusters. Both the theoretical and experimental results, together with existing data in the literature, show that some of the previous Fe(3+) band assignments in the spectra of Mars need to be revised. The theory of Fe(3+) spectra in minerals is discussed and applied to the spectrum of Mars.

  8. Research on the Terahertz Absorption Spectra of Histidine Enantiomer (L) and its Racemic Compound (DL).

    PubMed

    Zhou, Tao; Wu, Yidong; Cao, Juncheng; Zou, Liangliang; Yuan, Jie; Yao, Zhenwei; Xu, Gongjie

    2017-02-01

    Terahertz time-domain spectroscopy (THz-TDS) is used to investigate the absorption spectra of polycrystalline L- and DL-histidine in the frequency range of 10-100 cm(-1). The spectra exhibit distinct differences in peak frequencies between the enantiomer (L-histidine) and racemic compound (DL-histidine). The observed spectral differences are attributed to the intermolecular interactions. With the density function theory (DFT) method, the frequencies of vibrational modes of L-histidine and DL-histidine in the THz range are calculated and well assigned according to the measured spectra. The origin of the observed vibrational modes is found to be non-localized and of a collective (phonon-like) nature, which points to the lattice and skeleton vibrations mediated by the hydrogen bond. Furthermore, we propose and demonstrate a method for determining the composition ratio of histidine mixtures based on the THz absorption spectra.

  9. Theoretical analysis of electronic absorption spectra of vitamin B12 models

    NASA Astrophysics Data System (ADS)

    Andruniow, Tadeusz; Kozlowski, Pawel M.; Zgierski, Marek Z.

    2001-10-01

    Time-dependent density-functional theory (TD-DFT) is applied to analyze the electronic absorption spectra of vitamin B12. To accomplish this two model systems were considered: CN-[CoIII-corrin]-CN (dicyanocobinamide, DCC) and imidazole-[CoIII-corrin]-CN (cyanocobalamin, ImCC). For both models 30 lowest excited states were calculated together with transition dipole moments. When the results of TD-DFT calculations were directly compared with experiment it was found that the theoretical values systematically overestimate experimental data by approximately 0.5 eV. The uniform adjustment of the calculated transition energies allowed detailed analysis of electronic absorption spectra of vitamin B12 models. All absorption bands in spectral range 2.0-5.0 eV were readily assigned. In particular, TD-DFT calculations were able to explain the origin of the shift of the lowest absorption band caused by replacement of the-CN axial ligand by imidazole.

  10. THE STRUCTURE OF THE ULTRAVIOLET ABSORPTION SPECTRA OF CERTAIN PROTEINS AND AMINO ACIDS

    PubMed Central

    Coulter, Calvin B.; Stone, Florence M.; Kabat, Elvin A.

    1936-01-01

    1. The absorption spectra of a number of proteins in the region 2500 to 3000 A. have been found to comprise from six to nine narrow bands. In consequence of variation in the relative intensity of these bands from protein to protein, the absorption curve has a characteristic configuration for each protein. 2. These bands correspond closely in position with the narrow bands which appear in the absorption spectra of tryptophan, tyrosin, and phenylalanine. Tryptophan and tyrosin each present three bands, phenylalanine shows nine. 3. The bands in the proteins are accordingly attributed to these amino acids. In the proteins the bands are displaced from the positions which they occupy in the uncombined amino acids, in most instances, by 10 to 35 A. toward longer wavelengths. 4. The absorption spectrum of Pneumococcus Type I antibody resembles that of normal pseudoglobulin but shows characteristic differences. PMID:19872958

  11. Study of the absorption spectra of Fricke Xylenol Orange gel dosimeters

    SciTech Connect

    Gambarini, Grazia; Artuso, Emanuele; Liosi, Giulia Maria; Giacobbo, Francesca; Mariani, Mari; Brambilla, Luigi; Castiglioni, Chiara; Carrara, Mauro; Pignoli, Emanuele

    2015-07-01

    A systematic study of the absorption spectra of Fricke Xylenol Orange gel dosimeters has been performed, in the wavelength range from 300 nm to 700 nm. The spectrum of Xylenol Orange (without ferrous sulphate solution) has been achieved, in order to subtract its contribution from the absorption spectra of the irradiated Fricke Xylenol Orange gel dosimeters. The absorbance due to ferric ions chelated by Xylenol Orange has been studied for various irradiation doses. Two absorbance peaks are visible, mainly at low doses: the first peak increases with the dose more slowly than the second one. This effect can explain the apparent threshold dose that was frequently evidenced. (authors)

  12. Absorption Spectra of Broadened Sodium Resonance Lines in Presence of Rare Gases

    SciTech Connect

    Chung, H-K; Shurgalin, M; Babb, J F

    2002-09-11

    The pressure broadening of alkali-metal lines is a fundamental problem with numerous applications. For example, the sodium resonance lines broadened by xenon are important in the production of broad spectra emitted in the HPS (High-Pressure Sodium) lamp and they potentially can be used for gas condition diagnostics. Broadened absorption lines of alkali-metal atoms are prominent in the optical spectra of brown dwarfs and understanding the broadening mechanism will help elucidate the chemical composition and atmospheric properties of those stars. The far-line wing spectra of sodium resonance lines broadened by rare gases are found to exhibit molecular characteristics such as satellites and hence the total absorption coefficients for vapors of Na atoms and perturbing rare gas atoms can be modeled as Na-RG (rare gas) molecular absorption spectra. In this work, using carefully chosen interatomic potentials for Na-RG molecules we carry out quantum-mechanical calculations for reduced absorption coefficients for vapors composed of Na-He, Na-Ar, and Na-Xe. Calculated spectra are compared to available experimental results and the agreement is good in the measured satellite positions and shapes.

  13. A novel acoustic sensor approach to classify seeds based on sound absorption spectra.

    PubMed

    Gasso-Tortajada, Vicent; Ward, Alastair J; Mansur, Hasib; Brøchner, Torben; Sørensen, Claus G; Green, Ole

    2010-01-01

    A non-destructive and novel in situ acoustic sensor approach based on the sound absorption spectra was developed for identifying and classifying different seed types. The absorption coefficient spectra were determined by using the impedance tube measurement method. Subsequently, a multivariate statistical analysis, i.e., principal component analysis (PCA), was performed as a way to generate a classification of the seeds based on the soft independent modelling of class analogy (SIMCA) method. The results show that the sound absorption coefficient spectra of different seed types present characteristic patterns which are highly dependent on seed size and shape. In general, seed particle size and sphericity were inversely related with the absorption coefficient. PCA presented reliable grouping capabilities within the diverse seed types, since the 95% of the total spectral variance was described by the first two principal components. Furthermore, the SIMCA classification model based on the absorption spectra achieved optimal results as 100% of the evaluation samples were correctly classified. This study contains the initial structuring of an innovative method that will present new possibilities in agriculture and industry for classifying and determining physical properties of seeds and other materials.

  14. Infrared absorption spectra of molecular crystals: Possible evidence for small-polaron formation?

    NASA Astrophysics Data System (ADS)

    Pržulj, Željko; Čevizović, Dalibor; Zeković, Slobodan; Ivić, Zoran

    2008-09-01

    The temperature dependence of the position of the so-called anomalous band peaked at 1650cm in the IR-absorption spectrum of crystalline acetanilide (ACN) is theoretically investigated within the small-polaron theory. Its pronounced shift towards the position of the normal band is predicted with the rise of temperature. Interpretation of the IR-absorption spectra in terms of small-polaron model has been critically assessed on the basis of these results.

  15. X-ray absorption near-edge structure of GaN with high Mn concentration grown on SiC

    NASA Astrophysics Data System (ADS)

    Sancho-Juan, O.; Cantarero, A.; Garro, N.; Cros, A.; Martínez-Criado, G.; Salomé, M.; Susini, J.; Olguín, D.; Dhar, S.

    2009-07-01

    By means of x-ray absorption near-edge structure (XANES) several Ga1-xMnxN (0.03edges. All samples studied present a similar Mn ionization state, very close to 2+, and tetrahedral coordination. In order to interpret the near-edge structure, we have performed ab initio calculations using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of a Mn bonding \\mathrm {t_{2}}\\uparrow band localized in the gap region, and the corresponding anti-bonding state \\mathrm {t_{2}}\\downarrow , which seem to be responsible for the double structure which appears at the pre-edge absorption region. The shoulders and main absorption peak of the XANES spectra are attributed to transitions from the Mn(1s) band to the conduction bands, which are partially dipole allowed because of the Mn(4p) contribution to these bands.

  16. [Study on the effect of solar spectra on the retrieval of atmospheric CO2 concentration using high resolution absorption spectra].

    PubMed

    Hu, Zhen-Hua; Huang, Teng; Wang, Ying-Ping; Ding, Lei; Zheng, Hai-Yang; Fang, Li

    2011-06-01

    Taking solar source as radiation in the near-infrared high-resolution absorption spectrum is widely used in remote sensing of atmospheric parameters. The present paper will take retrieval of the concentration of CO2 for example, and study the effect of solar spectra resolution. Retrieving concentrations of CO2 by using high resolution absorption spectra, a method which uses the program provided by AER to calculate the solar spectra at the top of atmosphere as radiation and combine with the HRATS (high resolution atmospheric transmission simulation) to simulate retrieving concentration of CO2. Numerical simulation shows that the accuracy of solar spectrum is important to retrieval, especially in the hyper-resolution spectral retrieavl, and the error of retrieval concentration has poor linear relation with the resolution of observation, but there is a tendency that the decrease in the resolution requires low resolution of solar spectrum. In order to retrieve the concentration of CO2 of atmosphere, the authors' should take full advantage of high-resolution solar spectrum at the top of atmosphere.

  17. Models of optical absorption in amorphous semiconductors at the absorption edge — A review and re-evaluation

    NASA Astrophysics Data System (ADS)

    Ibrahim, A.; Al-Ani, S. K. J.

    1994-08-01

    Davis-Mott and Tauc models of optical absorption at the absorption edge in the high absorption coefficient region (104cm-1) are carefully reviewed with regard to their theoretical foundations, assumptions, mathematical derivations, and results. The full implications of these models are exploited, and it is found that the Davis-Mott model for negligible matrix elements between localised states could account for the cubic power law behaviour of with photon energy of some amorphous semiconductors such as a-Si. A fractional power law to find the optical band gapE opt, of the form [αħω ∝ (ħω-E opt)r; 2≤r≤3] based on Davis-Mott model is proposed in which the indexr can be a function of disorder. The Tauc model has further been extended to the case of negligible matrix elements between localised states, in which the same square power law forα vs.ħω with the same meaning of the optical gap as in the original Tauc model has resulted. A consideration of the case of unequal matrix elements for those transitions between localised states and those between extended states is also included. The meaning ofE opt has been re-assessed and it is emphasized that it is an extrapolation of delocalised states to the zero of the density of states rather than a threshold energy for the onset of some kind of optical transitions.

  18. New methodological approach for the vanadium K-edge X-ray absorption near-edge structure interpretation: application to the speciation of vanadium in oxide phases from steel slag.

    PubMed

    Chaurand, Perrine; Rose, Jérôme; Briois, Valérie; Salome, Murielle; Proux, Olivier; Nassif, Vivian; Olivi, Luca; Susini, Jean; Hazemann, Jean-Louis; Bottero, Jean-Yves

    2007-05-17

    This paper presents a comparison between several methods dedicated to the interpretation of V K-edge X-ray absorption near-edge structure (XANES) features. V K-edge XANES spectra of several V-bearing standard compounds were measured in an effort to evaluate advantages and limits of each method. The standard compounds include natural minerals and synthetic compounds containing vanadium at various oxidation state (from +3 to +5) and in different symmetry (octahedral, tetrahedral, and square pyramidal). Correlations between normalized pre-edge peak area and its centroid position have been identified as the most reliable method for determining quantitative and accurate redox and symmetry information for vanadium. This methodology has been previously developed for the Fe K edge. It is also well adapted for the V K edge and is less influenced by the standard choice than other methods. This methodology was applied on an "environmental sample," i.e., a well-crystallized leached steel slag containing vanadium as traces. Micro-XANES measurements allowed elucidating the microdistribution of vanadium speciation in leached steel slag. The vanadium exhibits an important evolution from the unaltered to the altered phases. Its oxidation state increases from +3 to +5 together with the decrease of its symmetry (from octahedral to tetrahedral).

  19. Search for CO absorption bands in IUE far-ultraviolet spectra of cool stars

    NASA Technical Reports Server (NTRS)

    Gessner, Susan E.; Carpenter, Kenneth G.; Robinson, Richard D.

    1994-01-01

    Observations of the red supergiant (M2 Iab) alpha Ori with the Goddard High Resolution Spectrograph (GHRS) on board the Hubble Space Telescope (HST) have provided an unambiguous detection of a far-ultraviolet (far-UV) chromospheric continuum on which are superposed strong molecular absorption bands. The absorption bands have been identified by Carpenter et al. (1994) with the fourth-positive A-X system of CO and are likely formed in the circumstellar shell. Comparison of these GHRS data with archival International Ultraviolet Explorer (IUE) spectra of alpha Ori indicates that both the continuum and the CO absorption features can be seen with IUE, especially if multiple IUE spectra, reduced with the post-1981 IUESIPS extraction procedure (i.e., with an oversampling slit), are carefully coadded to increase the signal to noise over that obtainable with a single spectrum. We therefore initiated a program, utilizing both new and archival IUE Short Wavelength Prime (SWP) spectra, to survey 15 cool, low-gravity stars, including alpha Ori, for the presence of these two new chromospheric and circumstellar shell diagnostics. We establish positive detections of far-UV stellar continua, well above estimated IUE in-order scattered light levels, in spectra of all of the program stars. However, well-defined CO absorption features are seen only in the alpha Ori spectra, even though spectra of most of the program stars have sufficient signal to noise to allow the dectection of features of comparable magnitude to the absorptions seen in alpha Ori. Clearly if CO is present in the circumstellar environments of any of these stars, it is at much lower column densities.

  20. Investigation of S H bonds in biologically important compounds by sulfur K-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prange, A.; Dahl, C.; Trüper, H. G.; Behnke, M.; Hahn, J.; Modrow, H.; Hormes, J.

    2002-09-01

    X-ray Absorption Near Edge Structure (XANES) spectroscopy, often provides a direct correlation between observed resonances in the spectrum and molecular bonds in the sample. This can be used as a fingerprint for the presence of a given molecular environment of the absorber atom in a sample. As the white line is found at similar energy positions for S C and S H bonds, this approach is impossible when both types of bond are present simultaneously, as often in biological systems. To develop a criterium for the presence of S H bonds in such samples, reduced glutathione, reduced coenzyme A, cysteine and their corresponding oxidized forms were investigated using sulfur K-edge XANES, revealing a unique feature at 2 475.8 eV in the respective difference spectra. To correlate this structure to S H bonds, H2S and H2S2 were measured, whose difference spectrum also shows a structure at this energy position, whereas it is not present throughout a variety of C S C/C S S C environments. Theoretical investigations suggest its correlation to a Rydberg transition occurring in the case of a S H bond. Using this criterium, the presence of S H bonds is in the purple sulfur bacterium Allochromatium vinosum during oxidation of intracellular accumulated sulfur, is proved, as expected from biological considerations.

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

    PubMed

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

    2015-09-01

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

  2. Absorption spectra and spectral-kinetic characteristics of the fluorescence of Sanguinarine in complexes with polyelectrolytes and DNA

    NASA Astrophysics Data System (ADS)

    Motevich, I. G.; Strekal, N. D.; Nowicky, J. W.; Maskevich, S. A.

    2010-07-01

    The absorption spectra and stationary and time resolved fluorescence spectra of the isoquinoline alkaloid sanguinarine are studied in aqueous media and during interactions with synthetic polyelectrolytes (polystyrene sulfonate and polyallylamine) and a natural polyelectrolyte (DNA).

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

    NASA Astrophysics Data System (ADS)

    Gatuzz, E.; García, J.; Mendoza, C.; Kallman, T. R.; Witthoeft, M.; Lohfink, A.; Bautista, M. A.; Palmeri, P.; Quinet, P.

    2013-05-01

    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 × 1021 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 & 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.

  4. [High-order derivative spectroscopy of infrared absorption spectra of the reaction centers from Rhodobacter sphaeroides].

    PubMed

    2005-01-01

    The infrared absorption spectra of reduced and chemically oxidized reaction center preparations from the purple bacterium Rhodobacter sphaeroides were investigated by means of high-order derivative spectroscopy. The model Gaussian band with a maximum at 810 nm and a half-band of 15 nm found in the absorption spectrum of the reduced reaction center preparation is eliminated after the oxidation of photoactive bacteriochlorophyll dimer (P). This band was related to the absorption of the P(+)y excitonic band of P. On the basis of experimental results, it was concluded that the bleaching of the P(+)y absorption band at 810 nm in the oxidized reaction center preparations gives the main contribution to the blue shift of the 800 nm absorption band of Rb. sphaeroides reaction centers.

  5. Excited states and absorption spectra of β-diketonate complexes of boron difluoride with aromatic substituents

    NASA Astrophysics Data System (ADS)

    Vovna, V. I.; Kazachek, M. V.; L'vov, I. B.

    2012-04-01

    In the approximation of the time-dependent electron density functional theory, we have studied using the quantum-chemical method the nature of excited states of boron difluoride acetylacetonate F2BAA and its substituted derivatives that contain aromatic groups with one or two benzene cycles in the β-position. Optimization of the geometry of complexes show coplanar positions of cycles for all compounds, except for that with the substituent C6H3(CH3)2. Based on the calculated transition energies and oscillator strengths, we have simulated the absorption spectra in the prevacuum range. The calculated absorption spectra have been compared with the experimental spectra in the gas phase or in solutions. We show that, in the absorption spectra of complexes that contain substituents with one benzene cycle, the first three bands are caused by the transition of π electrons of the substituent to the LUMO of the chelate cycle. In complexes with two cycles in the substituent, the number of these transitions increases to five. As the π system becomes more extended, a bathochromic shift of the first absorption band and an increase in the transition probability are observed.

  6. Absorption and fluorescence spectra of poly(p-phenylenevinylene) (PPV) oligomers: an ab initio simulation.

    PubMed

    Cardozo, Thiago M; Aquino, Adélia J A; Barbatti, Mario; Borges, Itamar; Lischka, Hans

    2015-03-05

    The absorption and fluorescence spectra of poly(p-phenylenevinylene) (PPV) oligomers with up to seven repeat units were theoretically investigated using the algebraic diagrammatic construction method to second order, ADC(2), combined with the resolution-of-the-identity (RI) approach. The ground and first excited state geometries of the oligomers were fully optimized. Vertical excitation energies and oscillator strengths of the first four transitions were computed. The vibrational broadening of the absorption and fluorescence spectra was studied using a semiclassical nuclear ensemble method. After correcting for basis set and solvent effects, we achieved a balanced description of the absorption and fluorescence spectra by means of the ADC(2) approach. This fact is documented by the computed Stokes shift along the PPV series, which is in good agreement with the experimental values. The experimentally observed band width of the UV absorption and fluorescence spectra is well reproduced by the present simulations showing that the nuclear ensemble generated should be well suitable for consecutive surface hopping dynamics simulations.

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

    ERIC Educational Resources Information Center

    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.

  8. In situ phytoplankton absorption, fluorescence emission, and particulate backscattering spectra determined from reflectance

    NASA Technical Reports Server (NTRS)

    Roesler, Collin S.; Pery, Mary Jane

    1995-01-01

    An inverse model was developed to extract the absortion and scattering (elastic and inelastic) properties of oceanic constituents from surface spectral reflectance measurements. In particular, phytoplankton spectral absorption coefficients, solar-stimulated chlorophyll a fluorescence spectra, and particle backscattering spectra were modeled. The model was tested on 35 reflectance spectra obtained from irradiance measurements in optically diverse ocean waters (0.07 to 25.35 mg/cu m range in surface chlorophyll a concentrations). The universality of the model was demonstrated by the accurate estimation of the spectral phytoplankton absorption coefficents over a range of 3 orders of magnitude (rho = 0.94 at 500 nm). Under most oceanic conditions (chlorophyll a less than 3 mg/cu m) the percent difference between measured and modeled phytoplankton absorption coefficents was less than 35%. Spectral variations in measured phytoplankton absorption spectra were well predicted by the inverse model. Modeled volume fluorescence was weakly correlated with measured chl a; fluorescence quantum yield varied from 0.008 to 0.09 as a function of environment and incident irradiance. Modeled particle backscattering coefficients were linearly related to total particle cross section over a twentyfold range in backscattering coefficents (rho = 0.996, n = 12).

  9. [Chlorine speciation and concentration in cultivated soil in the northeastern China studied by X-ray absorption near edge structure].

    PubMed

    Li, Jing; Lang, Chun-Yan; Ma, Ling-Ling; Xu, Dian-Dou; Zheng, Lei; Lu, Yu-Nanz; Cui Li-Rui; Zhang, Xiao-Meng

    2014-10-01

    A procedure has been proposed to determine chlorine speciation and concentration in soil with X-ray absorption near edge structure (XANES), and this method was applied to study the cultivated soil (bog, dark brown and black cultivated soil) in the Northeastern China. Qualitative analysis was carried out by least-squares fitting of sample spectra with standard spectra of three model compounds (NaCl, 3-chloropropionic acid, chlorophenol red). Linear correlation between the absolute fluorescence intensity of a series of NaCl standards and the Cl concentration was used as quantification standard for measuring the total Cl concentration in samples. The detection limits,relative standard deviation (RSD), recoveries were 2 mg · kg(-1), 0%-5% and 77%-133%, respectively. The average concentration of total Cl was 19 mg · kg(-1). The average relative content was as high as 61% of organochlorine with the concentration of 1-2 times as high as the concentration of inorganic chloride. The distribution trend of the total Cl, inorganic chloride and organic chlorine in different types of soil was: bog arable soil > dark brown soil > black soil. In conclusion, XANES is a reliable method to nondestructively characterize the speciation and concentration of chlorine in soil, which would provide some basic data for the future study of the chlorine's biogeochemical transformations.

  10. The effects of dust scattering on high-resolution X-ray absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, Lia; Garcia, Javier; Wilms, Joern; Baganoff, Frederick K.

    2016-04-01

    In high resolution X-ray spectroscopy, dust scattering significantly enhances the total extinction optical depth and alters the shape of photoelectric absorption edges. This effect is modulated by the dust grain size distribution, spatial location along the line of sight, and the imaging resolution of the X-ray telescope. We focus in particular on the Fe L-edge at 0.7 keV, fitting a template for the total extinction to the high resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. In cases where dust is intrinsic to the source, a covering factor based on the angular extent of the dusty material must be applied to the extinction curve, regardless of imaging resolution. We discuss the various astrophysical cases in which scattering effects need to be taken into account.

  11. The irradiation of ammonia ice studied by near edge x-ray absorption spectroscopy

    SciTech Connect

    Parent, Ph.; Bournel, F.; Lasne, J.; Laffon, C.; Carniato, S.; Lacombe, S.; Strazzulla, G.; Gardonio, S.; Lizzit, S.; Kappler, J.-P.; Joly, L.

    2009-10-21

    A vapor-deposited NH{sub 3} ice film irradiated at 20 K with 150 eV photons has been studied with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K-edge. Irradiation leads to the formation of high amounts (12%) of molecular nitrogen N{sub 2}, whose concentration as a function of the absorbed energy has been quantified to 0.13 molecule/eV. The stability of N{sub 2} in solid NH{sub 3} has been also studied, showing that N{sub 2} continuously desorbs between 20 and 95 K from the irradiated ammonia ice film. Weak concentrations (<1%) of other photoproducts are also detected. Our NEXAFS simulations show that these features own to NH{sub 2}, N{sub 2}H{sub 2}, and N{sub 3}{sup -}.

  12. Calibration and analysis of spatially resolved x-ray absorption spectra from a nonuniform plasma

    NASA Astrophysics Data System (ADS)

    Knapp, P. F.; Hansen, S. B.; Pikuz, S. A.; Shelkovenko, T. A.; Hammer, D. A.

    2012-07-01

    We report here the calibration and analysis techniques used to obtain spatially resolved density and temperature measurements of a pair of imploding aluminum wires from x-ray absorption spectra. A step wedge is used to measure backlighter fluence at the film, allowing transmission through the sample to be measured with an accuracy of ±14% or better. A genetic algorithm is used to search the allowed plasma parameter space and fit synthetic spectra with 20 μm spatial resolution to the measured spectra, taking into account that the object plasma nonuniformity must be physically reasonable. The inferred plasma conditions must be allowed to vary along the absorption path in order to obtain a fit to the spectral data. The temperature is estimated to be accurate to within ±25% and the density to within a factor of two. This information is used to construct two-dimensional maps of the density and temperature of the object plasma.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Cheng; Do, Thanh Nhut; Ong, Xuanwei; Chan, Yinthai; Tan, Howe-Siang

    2016-12-01

    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.

  14. Solvent and structural effects on the UV absorption spectra of N-(substituted phenyl)-2-cyanoacetamides.

    PubMed

    Matijević, Borko M; Vaštag, Đenđi Đ; Perišić-Janjić, Nada U; Apostolov, Suzana Lj; Milčić, Miloš K; Živanović, Lidija; Marinković, Aleksandar D

    2014-01-03

    UV absorption spectra of N-(substituted phenyl)-2-cyanoacetamides have been recorded in the range 200-400 nm in the set of selected solvents. The solute-solvent interactions were analyzed on the basis of linear solvation energy relationships (LSER) concept proposed by Kamlet and Taft. The effects of substituents on the absorption spectra were interpreted by correlation of absorption frequencies with Hammett substituent constant, σ. It was found that substituents significantly change the extent of conjugation. Furthermore, the experimental findings were interpreted with the aid of ab initio B3LYP/6-311G(d,p) method. Electronic energies was calculated by the use of 6-311++G(3df,3pd) methods with standard polarized continuum model (PCM) for inclusion of the solvent effect.

  15. Possible spinel absorption bands in S-asteroid visible reflectance spectra

    NASA Technical Reports Server (NTRS)

    Hiroi, T.; Vilas, F.; Sunshine, J. M.

    1994-01-01

    Minor absorption bands in the 0.55 to 0.7 micron wavelength range of reflectance spectra of 10 S asteroids have been found and compared with those of spinel-group minerals using the modified Gaussian model. Most of these S asteroids are consistently shown to have two absorption bands around 0.6 and 0.67 micron. Of the spinel-group minerals examined in this study, the 0.6 and 0.67 micron bands are most consistent with those seen in chromite. Recently, the existence of spinels has also been detected from the absorption-band features around 1 and 2 micron of two S-asteroid reflectance spectra, and chromite has been found in a primitive achondrite as its major phase. These new findings suggest a possible common existence of spinel-group minerals in the solar system.

  16. Radiatively driven winds for different power law spectra. [for explaining narrow and broad quasar absorption lines

    NASA Technical Reports Server (NTRS)

    Beltrametti, M.

    1980-01-01

    The analytic solutions for radiatively driven winds are given for the case in which the winds are driven by absorption of line and continuum radiation. The wind solutions are analytically estimated for different parameters of the central source and for different power law spectra. For flat spectra, three sonic points can exist; it is shown, however, that only one of these sonic points is physically realistic. Parameters of the central source are given which generate winds of further interest for explaining the narrow and broad absorption lines in quasars. For the quasar model presented here, winds which could give rise to the narrow absorption lines are generated by central sources with parameters which are not realistic for quasars.

  17. Delta bilirubin: absorption spectra, molar absorptivity, and reactivity in the diazo reaction.

    PubMed

    Doumas, B T; Wu, T W; Jendrzejczak, B

    1987-06-01

    Delta bilirubin (B delta), isolated from serum, has an absorption maximum near 440 nm and a molar absorptivity of 72,000 L mol-1cm-1 in either Tris HCl (0.1 mol/L, pH 8.5) or phosphate (0.13 mol/L, pH 7.4) buffer. This absorptivity exceeds by approximately 50% and 59%, respectively, that of unconjugated bilirubin in the same buffers. This finding suggests that substantial errors can be incurred in direct spectrophotometry of bilirubins in serum. In the total diazo (TBIL) assay (Clin Chem 1985;31:1779-89), the color yield from B delta increases by 10% as the final diazo concentration is increased from 0.27 to 0.81 mmol/L. In the direct (DBIL) assay, if done in HCl (50 mmol/L), B delta yields approximately 15% more color as the diazo concentration is increased from 0.51 to 1.53 mmol/L, whereas in acetate buffer (0.4 mol/L, pH 4.7) the corresponding color yield is 25% greater. However, the absolute color yield for the reaction in HCl exceeds that in acetate buffer. In both the TBIL and the DBIL assay, B delta reacts slowly, nearly complete reaction requiring 10 min. Thus, B delta may be seriously underestimated in diazo (especially DBIL) methods in which short reaction times (20 s to 1 min) are used.

  18. Origins of extreme broadening mechanisms in near-edge x-ray spectra of nitrogen compounds

    NASA Astrophysics Data System (ADS)

    Vinson, John; Jach, Terrence; Elam, W. T.; Denlinger, J. D.

    2014-11-01

    We demonstrate the observation of many-body lifetime effects in valence-band x-ray emission. A comparison of the N K α emission of crystalline ammonium nitrate to molecular-orbital calculations revealed an unexpected, extreme broadening of the NO σ recombination—so extensively as to virtually disappear. GW calculations establish that this disappearance is due to a large imaginary component of the self-energy associated with the NO σ orbitals. Building upon density-functional theory, we have calculated radiative transitions from the nitrogen 1 s level of ammonium nitrate and ammonium chloride using a Bethe-Salpeter method to include electron-hole interactions. The absorption and emission spectra of both crystals evince large, orbital-dependent sensitivity to molecular dynamics. We demonstrate that many-body effects as well as thermal and zero-point motion are vital for understanding observed spectra. A computational approach using average atomic positions and uniform broadening to account for lifetime and phonon effects is unsatisfactory.

  19. Three Dimensional Mapping of Nicle Oxidation States Using Full Field Xray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, G.J.; Chu, Y.; Harris, W.M.; Izzo, J.R.; Grew, K.N., Chiu, W.K.S.; Yi, J.; Andrews, J.C.; Liu, Y., Pierro, P.

    2011-04-28

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  20. L-edge X-ray absorption studies of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Bertram, S.; Kaindl, G.; Jové, J.; Pagès, M.

    1989-06-01

    The x-ray absorption near-edge structure (XANES) at the Np-L thresholds was investigated for Np compounds with formal valencies III to VII. At LIII, single and double-peaked white lines are observed corresponding to different final states that are populated through core excitation and 5f/ligand hybridization. For the non-metallic Np compounds studied, the weighted mean values of the LIII-XANES shifts relative to NpO2 exhibit a clear correlation with the isomer shifts of the 59-keV Mössbauer resonance of 237Np.

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

    USGS Publications Warehouse

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

    2011-01-01

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

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

    USGS Publications Warehouse

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

    2014-01-01

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

  3. Computer Simulation of the far Infrared Collision Induced Absorption Spectra of Gaseous CO2

    NASA Technical Reports Server (NTRS)

    Gruszka, Marcin; Borysow, Aleksandra

    1998-01-01

    Far infrared collision induced absorption spectra of gaseous CO2 were computed using molecular dynamics simulations. The quadrupole and hexadecapole multipolar induction, through the trace, and the anisotropy of the molecular polarizability were found to be insufficient to represent properly the dipole induction mechanism. For a detailed analysis of the induction process the spectra obtained were decomposed into components resulting from different terms of the induced dipole. Based on this decomposition, all additional overlap contribution for each term was proposed. When spectra were recomputed including such overlap, good agreement between experiment and simulation was achieved over the temperature range at which measurements exist (233-400 K). The use of an anisotropic intermolecular potential was found to be of critical importance for obtaining the right shape of the far wings of the spectra.

  4. Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics.

    PubMed

    Ikeda, Takashi

    2014-07-28

    From both the polarized and depolarized Raman scattering spectra of supercritical water a peak located at around 1600 cm(-1), attributed normally to bending mode of water molecules, was experimentally observed to vanish, whereas the corresponding peak remains clearly visible in the measured infrared (IR) absorption spectrum. In this computational study a theoretical formulation for analyzing the IR and Raman spectra is developed via first principles molecular dynamics combined with the modern polarization theory. We demonstrate that the experimentally observed peculiar behavior of the IR and Raman spectra for water are well reproduced in our computational scheme. We discuss the origins of a feature observed at 1600 cm(-1) in Raman spectra of ambient water.

  5. SimBAL: A Spectral Synthesis Approach to Analyzing Broad Absorption Line Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Terndrup, Donald M.; Leighly, Karen; Gallagher, Sarah; Richards, Gordon T.

    2017-01-01

    Broad Absorption Line quasars (BALQSOs) show blueshifted absorption lines in their rest-UV spectra, indicating powerful winds emerging from the central engine. These winds are essential part of quasars: they can carry away angular momentum and thus facilitate accretion through a disk, they can distribute chemically-enriched gas through the intergalactic medium, and they may inject kinetic energy to the host galaxy, influencing its evolution. The traditional method of analyzing BALQSO spectra involves measuring myriad absorption lines, computing the inferred ionic column densities in each feature, and comparing with the output of photonionization models. This method is inefficient and does not handle line blending well. We introduce SimBAL, a spectral synthesis fitting method for BALQSOs, which compares synthetic spectra created from photoionization model results with continuum-normalized observed spectra using Bayesian model calibration. We find that we can obtain an excellent fit to the UV to near-IR spectrum of the low-redshift BALQSO SDSS J0850+4451, including lines from diverse ionization states such as PV, CIII*, SIII, Lyalpha, NV, SiIV, CIV, MgII, and HeI*.

  6. THERMAL ABSORPTION AS THE CAUSE OF GIGAHERTZ-PEAKED SPECTRA IN PULSARS AND MAGNETARS

    SciTech Connect

    Lewandowski, Wojciech; Rożko, Karolina; Kijak, Jarosław; Melikidze, George I.

    2015-07-20

    We present a model that explains the observed deviation of the spectra of some pulsars and magnetars from the power-law spectra that are seen in the bulk of the pulsar population. Our model is based on the assumption that the observed variety of pulsar spectra can be naturally explained by the thermal free–free absorption that takes place in the surroundings of the pulsars. In this context, the variety of the pulsar spectra can be explained according to the shape, density, and temperature of the absorbing media and the optical path of the line of sight across it. We have put specific emphasis on the case of the radio magnetar SGR J1745–2900 (also known as the Sgr A* magnetar), modeling the rapid variations of the pulsar spectrum after the outburst of 2013 April as due to the free–free absorption of the radio emission in the electron material ejected during the magnetar outburst. The ejecta expands with time and consequently the absorption rate decreases and the shape of the spectrum changes in such a way that the peak frequency shifts toward the lower radio frequencies. In the hypothesis of an absorbing medium, we also discuss the similarity between the spectral behavior of the binary pulsar B1259–63 and the spectral peculiarities of isolated pulsars.

  7. Modeling absorption spectra for detection of the combustion products of jet engines by laser remote sensing.

    PubMed

    Voitsekhovskaya, Olga K; Kashirskii, Danila E; Egorov, Oleg V; Shefer, Olga V

    2016-05-10

    The absorption spectra of exhaust gases (H2O, CO, CO2, NO, NO2, and SO2) and aerosol (soot and Al2O3) particles were modeled at different temperatures for the first time and suitable spectral ranges were determined for conducting laser remote sensing of the combustion products of jet engines. The calculations were conducted on the basis of experimental concentrations of the substances and the sizes of the aerosol particles. The temperature and geometric parameters of jet engine exhausts were also taken from the literature. The absorption spectra were obtained via the line-by-line method, making use of the spectral line parameters from the authors' own high-temperature databases (for NO2 and SO2 gases) and the HITEMP 2010 database, and taking into account atmospheric transmission. Finally, the theoretical absorption spectra of the exhaust gases were plotted at temperatures of 400, 700, and 1000 K, and the impact of aerosol particles on the total exhaust spectra was estimated in spectral ranges suitable for remote sensing applications.

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

    NASA Astrophysics Data System (ADS)

    Kokaly, Raymond F.; Skidmore, Andrew K.

    2015-12-01

    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 Csbnd 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 spectral influences

  9. Tailoring of absorption edge by thermal annealing in tin oxide thin films

    SciTech Connect

    Thakur, Anup; Gautam, Sanjeev; Kumar, Virender; Chae, K. H.; Lee, Ik-Jae; Shin, Hyun Joon

    2015-05-15

    Tin oxide (SnO{sub 2}) thin films were deposited by radio-frequency (RF) magnetron sputtering on silicon and glass substrates in different oxygen-to-argon gas-flow ratio (O{sub 2}-to-Ar = 0%, 10%, 50%). All films were deposited at room temperature and fixed working pressures, 10 mTorr. The X-ray diffraction (XRD) measurement suggests that all films were crystalline in nature except film deposited in argon environment. Thin films were annealed in air at 200 °C, 400 °C and 600 °C for two hours. All films were highly transparent except the film deposited only in the argon environment. It was also observed that transparency was improved with annealing due to decrease in oxygen vacancies. Atomic force microscopy (AFM), results showed that the surface of all the films were highly flat and smooth. Blue shift was observed in the absorption edge with annealing temperature. It was also observed that there was not big change in the absorption edge with annealing for films deposited in 10% and 50% oxygen-to-argon gas-flow ratio.

  10. Vibrational dynamics of DNA. II. Deuterium exchange effects and simulated IR absorption spectra

    NASA Astrophysics Data System (ADS)

    Lee, Chewook; Cho, Minhaeng

    2006-09-01

    In Paper I, we studied vibrational properties of normal bases, base derivatives, Watson-Crick base pairs, and multiple layer base pair stacks in the frequency range of 1400-1800cm-1. However, typical IR absorption spectra of single- and double-stranded DNA have been measured in D2O solution. Consequently, the more relevant bases and base pairs are those with deuterium atoms in replacement with labile amino hydrogen atoms. Thus, we have carried out density functional theory vibrational analyses of properly deuterated bases, base pairs, and stacked base pair systems. In the frequency range of interest, both aromatic ring deformation modes and carbonyl stretching modes appear to be strongly IR active. Basis mode frequencies and vibrational coupling constants are newly determined and used to numerically simulate IR absorption spectra. It turns out that the hydration effects on vibrational spectra are important. The numerically simulated vibrational spectra are directly compared with experiments. Also, the O18-isotope exchange effect on the poly(dG):poly(dC) spectrum is quantitatively described. The present calculation results will be used to further simulate two-dimensional IR photon echo spectra of DNA oligomers in the companion Paper III.

  11. Absorption spectra and light penetration depth of normal and pathologically altered human skin

    NASA Astrophysics Data System (ADS)

    Barun, V. V.; Ivanov, A. P.; Volotovskaya, A. V.; Ulashchik, V. S.

    2007-05-01

    A three-layered skin model (stratum corneum, epidermis, and dermis) and engineering formulas for radiative transfer theory are used to study absorption spectra and light penetration depths of normal and pathologically altered skin. The formulas include small-angle and asymptotic approximations and a layer-addition method. These characteristics are calculated for wavelengths used for low-intensity laser therapy. We examined several pathologies such as vitiligo, edema, erythematosus lupus, and subcutaneous wound, for which the bulk concentrations of melanin and blood vessels or tissue structure (for subcutaneous wound) change compared with normal skin. The penetration depth spectrum is very similar to the inverted blood absorption spectrum. In other words, the depth is minimal at blood absorption maxima. The calculated absorption spectra enable the power and irradiation wavelength providing the required light effect to be selected. Relationships between the penetration depth and the diffuse reflectance coefficient of skin (unambiguously expressed through the absorption coefficient) are analyzed at different wavelengths. This makes it possible to find relationships between the light fields inside and outside the tissue.

  12. Temperature variation of the fundamental absorption edge in AgGaSe 2

    NASA Astrophysics Data System (ADS)

    Calderón, E.; Fernández, B.; Durán, L.; Grima, P.; Morocoima, M.; Quintero, E.; Rincón, C.; Quintero, M.

    2009-11-01

    Optical absorption measurements were made in the temperature range 9-300 K on the chalcopyrite semiconductor compound AgGaSe 2 and the optical energy gap EG determined as a function of temperature T. In order to obtain the values of EG as a function of T, the Elliot-Toyozawa model [R.J. Elliot, J. Phys. Rev. 108 (1957) 1384; D.D. Sell, P. Lawaets, Phys. Rev. Lett. 26 (1971) 311] was employed to perform the analysis of the optical absorption spectra. The resulting EG vs. T curve was fitted to a semi-empirical model that takes into account both the thermal expansion and the electron-phonon interaction contributions. The results have been used to estimate values of the deformation potentials of the valence and conduction bands of the compound.

  13. Remote sensing of trace constituents from atmospheric infrared emission and absorption spectra

    NASA Technical Reports Server (NTRS)

    Barker, D. B.; Brooks, J. N.; Goldman, A.; Kosters, J. J.; Murcray, D. G.; Murcray, F. H.; Van Allen, J.; Williams, W. J.

    1976-01-01

    Atmospheric infrared emission and absorption spectra obtained from aircraft and balloon-borne spectrometers are presented. From such spectra, mixing ratio vs altitude profiles are derived for several minor constituents. Recent results for HNO3, CF2Cl2, CFCl3, and HF are presented. In addition, the feasibility of infrared detection of other trace constituents, such as HCl, HF, NH3, NO and SO2, against the rest of the atmospheric background is studied. From this study, made on a line-by-line basis for 'state of the art' airborne spectrometers, potential spectral features for detection of the trace constituents are isolated.

  14. Optical Absorption Spectra of Ternary Complex of Praseodymium in Different Environment

    NASA Astrophysics Data System (ADS)

    Gupta, Anup Kumar; Ujjwal, Shri Kishan

    The optical absorption spectra of complex of Praseodymium in different solvents i.e water, Methanol, Ethanol & Acetic Acid have been recorded in visible region (360-620 nm for Pr3+) using amino acid as primary ligand and diol as secondary ligand. The value of energies & intensities of various transitions have been calculated using Judd-Ofelt relation is in good agreement with experimental result. The study of complex found it to be covalent in nature. The spectra in visible region have been recorded on model uv-2601 Rayleigh analytical instrument corp.

  15. Identification of acetylene (C2H2) in infrared atmospheric absorption spectra

    NASA Astrophysics Data System (ADS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Gillis, J. R.; Bonomo, F. S.; Murcray, F. H.; Murcray, D. G.; Cicerone, R. J.

    1981-12-01

    Infrared atmospheric absorption spectra at ˜0.02 cm-1 resolution obtained during a balloon flight made on March 23, 1981, show absorption features attributable to C2H2. These features are used to derive a preliminary mixing ratio of ˜25 pptv near 9 km. This mixing ratio falls into the range of values we calculate for upper tropospheric C2H2 in a photochemical/transport model but well below values measured previously in samples collected by other researchers.

  16. Identification of acetylene /C2H2/ in infrared atmospheric absorption spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Gillis, J. R.; Bonomo, F. S.; Murcray, F. H.; Murcray, D. G.; Cicerone, R. J.

    1981-01-01

    Infrared atmospheric absorption spectra at 0.02/cm resolution were obtained during a balloon flight on March 23, 1981 from the Holloman AFB, New Mexico. The absorption features, attributed to C2H2, were used to derive a preliminary mixing ratio of about 25 pptv near 9 km, accurate to + or - 40%. This mixing ratio falls into the range of values calculated for the upper troposphere C2H2 in a photochemical/transport model. However, previous measurements from aircraft grab sampling (Cronn and Robinson, 1979) show four to twelve times this C2H2 concentration 1.5 km below the tropopause.

  17. In vivo low-coherence spectroscopic measurements of local hemoglobin absorption spectra in human skin

    NASA Astrophysics Data System (ADS)

    Bosschaart, Nienke; Faber, Dirk J.; van Leeuwen, Ton G.; Aalders, Maurice C. G.

    2011-10-01

    Localized spectroscopic measurements of optical properties are invaluable for diagnostic applications that involve layered tissue structures, but conventional spectroscopic techniques lack exact control over the size and depth of the probed tissue volume. We show that low-coherence spectroscopy (LCS) overcomes these limitations by measuring local attenuation and absorption coefficient spectra in layered phantoms. In addition, we demonstrate the first in vivo LCS measurements of the human epidermis and dermis only. From the measured absorption in two distinct regions of the dermal microcirculation, we determine total hemoglobin concentration (3.0+/-0.5 g/l and 7.8+/-1.2 g/l) and oxygen saturation.

  18. Intervening Mg II absorption systems from the SDSS DR12 quasar spectra

    NASA Astrophysics Data System (ADS)

    Raghunathan, Srinivasan; Clowes, Roger G.; Campusano, Luis E.; Söchting, Ilona K.; Graham, Matthew J.; Williger, Gerard M.

    2016-12-01

    We present the catalogue of the Mg II absorption systems detected at a high significance level using an automated search algorithm in the spectra of quasars from the 12th data release of the Sloan Digital Sky Survey. A total of 266,433 background quasars were searched for the presence of absorption systems in their spectra. The continuum modelling for the quasar spectra was performed using a mean filter. A pseudo-continuum derived using a median filter was used to trace the emission lines. The absorption system catalogue contains 39,694 Mg II systems detected at a 6.0, 3.0σ level respectively for the two lines of the doublet. The catalogue was constrained to an absorption line redshift of 0.35 ≤ z2796 ≤ 2.3. The rest-frame equivalent width of the λ2796 line ranges between 0.2 ≤ Wr ≤ 6.2 Å. Using Gaussian noise-only simulations, we estimate a false positive rate of 7.7 per cent in the catalogue. We measured the number density ∂N2796/∂z of Mg II absorbers and find evidence for steeper evolution of the systems with Wr ≥ 1.2 Å at low redshifts (z2796 ≤ 1.0), consistent with other earlier studies. A suite of null tests over the redshift range 0.5 ≤ z2796 ≤ 1.5 was used to study the presence of systematics and selection effects like the dependence of the number density evolution of the absorption systems on the properties of the background quasar spectra. The null tests do not indicate the presence of any selection effects in the absorption catalogue if the quasars with spectral signal-to-noise level less than 5.0 are removed. The resultant catalogue contains 36,981 absorption systems. The Mg II absorption catalogue is publicly available and can be downloaded from the link http://srini.ph.unimelb.edu.au/mgii.php.

  19. In vivo low-coherence spectroscopic measurements of local hemoglobin absorption spectra in human skin.

    PubMed

    Bosschaart, Nienke; Faber, Dirk J; van Leeuwen, Ton G; Aalders, Maurice C G

    2011-10-01

    Localized spectroscopic measurements of optical properties are invaluable for diagnostic applications that involve layered tissue structures, but conventional spectroscopic techniques lack exact control over the size and depth of the probed tissue volume. We show that low-coherence spectroscopy (LCS) overcomes these limitations by measuring local attenuation and absorption coefficient spectra in layered phantoms. In addition, we demonstrate the first in vivo LCS measurements of the human epidermis and dermis only. From the measured absorption in two distinct regions of the dermal microcirculation, we determine total hemoglobin concentration (3.0±0.5 g∕l and 7.8±1.2 g∕l) and oxygen saturation.

  20. Measurements of trace constituents from atmospheric infrared emission and absorption spectra, a feasibility study

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Williams, W. J.; Murcray, D. G.

    1974-01-01

    The feasibility of detecting eight trace constituents (CH4, HCl, HF, HNO3, NH3, NO, NO2 and SO2) against the rest of the atmospheric background at various altitudes from infrared emission and absorption atmospheric spectra was studied. Line-by-line calculations and observational data were used to establish features that can be observed in the atmospheric spectrum due to each trace constituent. Model calculations were made for experimental conditions which approximately represent state of the art emission and absorption spectrometers.

  1. Theoretical analysis of x-ray-absorption near-edge fine structure at the O and metal K edges of LaFeO{sub 3} and LaCoO{sub 3}

    SciTech Connect

    Wu, Z.Y.; Pedio, M.; Cimino, R.; Mobilio, S. |; Barman, S.R. |; Maiti, K.; Sarma, D.D. |

    1997-07-01

    We present experimental x-ray-absorption spectra at the oxygen and 3d transition-metal K edges of LaFeO{sub 3} and LaCoO{sub 3}. We interpret the experimental results in terms of detailed theoretical calculations based on multiple-scattering theory. Along with providing an understanding of the origin of various experimental features, we investigate the effects of structural distortions and the core-hole potential in determining the experimental spectral shape. The results indicate that the core-hole potential as well as many-body effects within the valence electrons do not have any strong effect on the spectra suggesting that the spectral features can be directly interpreted in terms of the electronic structure of such compounds. {copyright} {ital 1997} {ital The American Physical Society}

  2. Scalar and vector collisional interference in the vibration-rotation absorption spectra of H2 and HD

    NASA Technical Reports Server (NTRS)

    Herman, R. M.

    1987-01-01

    The only atomic or molecular spectra known to exhibit 'collisional interference' effects are those of H2 and its isotopes. Attention is presently given to the sharp absorption spectra of HD, which demonstrate collisional interference effects is a fashion that while surprising has been experimentally verified and theoretically characterized in detail. Collisional interference can dramatically alter the line shapes usually encountered in dipole absorption spectra, while nevertheless remaining narrow.

  3. Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

    NASA Technical Reports Server (NTRS)

    Du, Ping

    1993-01-01

    As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

  4. Analyzing absorption and scattering spectra of micro-scale structures with spectroscopic optical coherence tomography.

    PubMed

    Yi, Ji; Gong, Jianmin; Li, Xu

    2009-07-20

    We demonstrate the feasibility of characterizing the absorption and scattering spectra of micron-scale structures in a turbid medium using a spectroscopic optical coherence tomography (SOCT) system with a bandwidth of 430-650 nm. SOCT measurements are taken from phantoms composed of fluorescent microspheres. The absorption and scattering spectra are recovered with proper selections of spatial window width in the post processing step. Furthermore, we present an analysis using numerical OCT simulation based on full-wave solutions of the Maxwell's Equation to elucidate the origination of the multiple peaks in the OCT image for a single microsphere. Finally, we demonstrate the possibility of identifying contrast agents concentrated in micron-sized scale in an SOCT image. Two different types of microspheres in gel phantom are discriminated based on their distinguished absorbent feature.

  5. Far-ultraviolet absorption spectra of quasars: How to find missing hot gas and metals

    NASA Technical Reports Server (NTRS)

    Verner, D. A.; Tytler, David; Barthel, P. D.

    1994-01-01

    We show that some high-redshift QSO absorption systems that reveal only the H I Lyman series lines at wavelengths visible from the ground maybe a new class of ultra-high-ionization metal line systems, with metal lines in the far-UV region which is now being explored with satellites. At high temperatures or in intense radiation fields metal systems will not show the usual C IV absorption, and O VI will become the most prominent metal absorber. At still higher ionization, O IV also becomes weak and the strongest metal lines are from Ne VIII, Mg X and Si XII, which have doublets in the rangs 500-800 A. Hence very high ionization metal systems will not show metal lines in existing spectra. Recent X-ray observations show that galaxy halos contain hot gas, so we predict that far-UV spectra of QSOs will also show this gas.

  6. Three-dimensional time-dependent wave-packet calculations of OBrO absorption spectra

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Sun, Zhigang; Cong, Shu-Lin; Lou, Nanquan

    2005-08-01

    The absorption spectra of the C(A22)←X(B12) transition of the OBrO molecule are calculated using three-dimensional time-dependent wave-packet method in Radau coordinates for a total angular momentum J =0. The wave packet is propagated using the split operator technique associated with fast Fourier transform. Employing the basis functions obtained by one-dimensional Fourier grid Hamiltonian method, the initial wave packet is calculated directly on the three-dimensional Fourier grid. The numerical model is characterized by simplicity and efficiency. The ab initio potential surfaces for the C(A22) and X(B12) states are used in the calculation. The calculated absorption spectra of the C(A22)←X(B12) transition of OBrO molecule agree well with the experimental results.

  7. Observationally determined Fe II oscillator strengths. [interstellar and quasar absorption spectra

    NASA Technical Reports Server (NTRS)

    Van Steenberg, M.; Shull, J. M.; Seab, C. G.

    1983-01-01

    Absorption oscillator strengths for 21 Fe II resonance lines, have been determined using a curve-of-growth analysis of interstellar data from the Copernicus and International Ultraviolet Explorer (IUE) satellites. In addition to slight changes in strengths of the far-UV lines, new f-values are reported for wavelength 1608.45, a prominent line in interstellar and quasar absorption spectra, and for wavelength 2260.08, a weak, newly identified linen in IUE interstellar spectra. An upper limit on the strength of the undetected line at 2366.867 A (UV multiplet 2) is set. Using revised oscillator strengths, Fe II column densities toward 13 OB stars are derived. The interstellar depletions, (Fe/H), relative to solar values range between factors of 10 and 120.

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

    DTIC Science & Technology

    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...Trabalhador Saocarlense 400 Sao Carlos, SP, 13566-590 Brazil 8. PERFORMING ORGANIZATION REPORT NUMBER Report 3 - Final 9. SPONSORING/MONITORING AGENCY

  9. Emission and absorption spectra of some bridged 1,5-benzodiazepines

    NASA Astrophysics Data System (ADS)

    Mellor, J. M.; Pathirana, R. N.; Stibbard, J. H. A.

    Absorption spectra in neutral and acidic media are reported for a series of bridged 1,5-benzodiazepines, which are unable to tautomerize. Comparison is made with non-bridged 1,5-benzodiazepines capable of tautomeric rearrangement. Both bridged and non-bridged 1,5-benzodiazepines are essentially non-fluorescent due to the "proximity effect" of interaction between singlet ηπ* and ππ* states of similar energy, a phenomenon previously recognised in six-membered nitrogen heterocycles.

  10. Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density Functional Theory

    DTIC Science & Technology

    2013-08-20

    the calculated absorption spectra of isolated molecules can help to identify intramolecular vibrational modes of various materials. A series of...Transformation A molecule in 3-dimensions has a total of 3N-6 normal mode vibrations . The Schrodinger equation for the harmonic...oscillations of these normal modes has known solutions. The quantum mechanical spectrum of each of these vibrations is given in the harmonic approximation

  11. Ab initio study of optical absorption spectra of semiconductors and conjugated polymers

    SciTech Connect

    Tiago, M.L.; Chang, Eric K.; Rohlfing, Michael; Louie, Steven G.

    2000-04-30

    The effects of electron-hole interaction on the optical properties of a variety of materials have been calculated using an ab initio method based on solving the Bethe-Salpeter equation. Results on selected semiconductors, insulators, and semiconducting polymers are presented. In the cases of alpha-quartz (SiO2) and poly-phenylene-vinylene, resonant excitonic states qualitatively alter the absorption spectra.

  12. Algae (Microcystis and Scenedesmus) absorption spectra and its application on Chlorophyll a retrieval

    NASA Astrophysics Data System (ADS)

    Wu, Di; Chen, Maosi; Wang, Qiao; Gao, Wei

    2013-12-01

    Blue algae and green algae are the dominant phytoplankton groups that contribute to the eutrophication and the water bloom in inland water of China. The absorption coefficients (spectra) of the algae, which do not change with its intrinsic optical characteristics and the observation geometry, are strictly additive quantities. The characteristics of the absorption spectra of the two algae are presented. The pure blue algae and the pure green algae cultured in the laboratory environment are diluted and mixed at ten volume ratios. The Quantitative Filter Technique was applied to measure their absorption spectra. The "hot-ethanol extraction" method was chosen to calculate their concentration of Chlorophyll a. The retrieval algorithm developed in this study extracts the mapping information between each individual alga and their Chlorophyll a concentration via Continuous Wavelet Transform, and retrieves the Chlorophyll a concentration of each alga in their mixture using a trust region optimizer. The results show that the retrieved and the measured Chlorophyll a concentrations of the blue algae and the green algae components in the ten mixture match well with the average relative error of 5.55%.

  13. Near infrared cavity enhanced absorption spectra of atmospherically relevant ether-1, 4-Dioxane

    NASA Astrophysics Data System (ADS)

    Chandran, Satheesh; Varma, Ravi

    2016-01-01

    1, 4-Dioxane (DX) is a commonly found ether in industrially polluted atmosphere. The near infrared absorption spectra of this compound has been recorded in the region 5900-8230 cm- 1 with a resolution of 0.08 cm- 1 using a novel Fourier transform incoherent broadband cavity-enhanced absorption spectrometer (FT-IBBCEAS). All recorded spectra were found to contain regions that are only weakly perturbed. The possible combinations of fundamental modes and their overtone bands corresponding to selected regions in the measured spectra are tabulated. Two interesting spectral regions were identified as 5900-6400 cm- 1 and 8100-8230 cm- 1. No significant spectral interference due to presence of water vapor was observed suggesting the suitability of these spectral signatures for spectroscopic in situ detection of DX. The technique employed here is much more sensitive than standard Fourier transform spectrometer measurements on account of long effective path length achieved. Hence significant enhancement of weaker absorption lines above the noise level was observed as demonstrated by comparison with an available measurement from database.

  14. Modeling of multi-exciton transient absorption spectra of protochlorophyllide aggregates in aqueous solution.

    PubMed

    Sytina, Olga A; Novoderezhkin, Vladimir I; van Grondelle, Rienk; Groot, Marie Louise

    2011-11-03

    Protochlorophyllide (Pchlide) is a natural porphyrin, a precursor of chlorophyll, synthesized by plants for its photosynthetic apparatus. The pigment spontaneously forms aggregates when dissolved in neat water solution. We present here calculations of the transient absorption spectra and its comprising components (ground-state bleach, stimulated emission, and excited-state absorption) for a strongly excitonically coupled linear chain of four Pchlide chromophores, using exciton theory with phenomenological Gaussian line shapes and without energetic disorder. A refined multiexciton model that includes static disorder is applied to fit the experimental power-dependent transient absorption spectra of aqueous protochlorophyllide and the kinetics for delay times up to 20 ps after photoexcitation. We show that population up to the 4-exciton manifold is sufficient to explain the pronounced saturation of the bleaching and the shape changes in the instantaneous, t = 0.2 ps transient spectra when the pulse energy is increased from 10 to 430 nJ per pulse. The decay of the multiexciton manifold is relatively slow and is preceded by a spectroscopically distinct process. We suggest that the exciton states in the Pchlide aggregates are mixed with charge-transfer states (CTS) and that the population and repopulation of the CTS coupled to the exciton states explains the relatively slow decay of the multiexciton manifold. The relevance of our results to the optical properties and dynamics of natural photosynthetic complexes and the possible physical origin of CTS formation are discussed.

  15. The electronic absorption spectra of pyridine azides, solvent-solute interaction.

    PubMed

    Abu-Eittah, Rafie H; Khedr, Mahmoud K

    2009-01-01

    The electronic absorption spectra of: 2-, 3-, and 4-azidopyridines have been investigated in a wide variety of polar and non-polar solvents. According to Onsager model, the studied spectra indicate that the orientation polarization of solvent dipoles affects the electronic spectrum much stronger than the induction polarization of solvent dipoles. The effect of solvent dipole moment predominates that of solvent refractive index in determining the values of band maxima of an electronic spectrum. The spectra of azidopyridines differ basically from these of pyridine or mono-substituted pyridine. Results at hand indicate that the azide group perturbs the pyridine ring in the case of 3-azidopyridine much more than it does in the case of 2-azidopyridine. This result agrees with the predictions of the resonance theory. Although the equilibrium <==> azide tetrazole is well known, yet the observed spectra prove that such an equilibrium does not exist at the studied conditions. The spectra of the studied azidopyridines are characterized by the existence of overlapping transitions. Gaussian analysis is used to obtain nice, resolved spectra. All the observed bands correspond to pi-->pi* transitions, n-->pi* may be overlapped with the stronger pi-->pi* ones.

  16. Hot Experimental Absorption Spectra of CH_4 in the Pentad and Octad Region

    NASA Astrophysics Data System (ADS)

    Hargreaves, Robert J.; Dulick, Michael; Bernath, Peter F.

    2014-06-01

    We present comprehensive line lists of CH_4 at high temperatures for the pentad and octad region (2400-5000 wn). These spectra improve on our previous emission measurements for this region by using a new quartz sample cell in conjunction with a tube furnace (pictured). Ten temperatures have been recorded from room temperature up to 1000°C and our technique involves the acquisition of four separate Fourier transform infrared spectra at each temperature, thus accounting for both the emission and absorption of the molecule and the cell. By combining these four spectra we obtain true transmission spectra of hot CH_4 in this region. Analysis of this set of spectra enables the production of a line list that includes the position, intensity and empirical lower state energy. Our spectra and line lists can be used directly to model planetary atmospheres and brown dwarfs. Hargreaves, R.J., Beale, C.A., Michaux, L., Irfan, M., & Bernath, P.F. 2012, ApJ, 757, 46

  17. Theoretical Analysis on X-ray Absorption Spectra of Ti compounds as Catalysts in Lithium Amide-Imide reactions

    NASA Astrophysics Data System (ADS)

    Tsumuraya, Takao; Shishidou, Tatsuya; Oguchi, Tamio

    2008-03-01

    Solid-state storage is conceptually efficient approach for on-board vehicular hydrogen storage. In this context, light-element materials such as lithium amide LiNH2 and lithium imide Li2NH have been attracted much attention due to their high gravimetric densities of hydrogen. Recently, various transition-metal compounds have been examined with ball-milling technique for exploring catalysts to improve the hydrogen storage and desorption kinetics, and it is found that a small amount (1mol%) of titanium compounds revealed a superior effect in hydrogen desorption reaction LiNH2 + LiH -> Li2NH + H2 [1]. However, these catalysis mechanism and role of Ti in the reaction remain unanswered. Isobe et al. have carried out measurements of X-ray absorption spectroscopy(XAS) at Ti K-edge to see the electronic states of Ti recently [2]. In this paper, we calculate the electronic structure of Ti metal and its compounds, and obtained theoretical spectra to compare with the measured spectra by using first-principles calculations based on the all-electron FLAPW method. We discuss chemical bonding and local geometry of catalytically active states in the reaction. [1] T. Ichikawa, S. Isobe, N. Hanada and H. Fujii, J. of Alloys and Comp. 365, 271 (2004) . [2] S. Isobe, T. Ichikawa, Y. Kojima and H. Fujii, J. of Alloys and Comp. 446-447, 360 (2007).

  18. Structural Disorder in Colloidal InAs and CdSe Nanocrystals Observed by X-Ray Absorption Near-Edge Spectroscopy

    SciTech Connect

    Hamad, K.S.; Hamad, K.S.; Roth, R.; Roth, R.; Rockenberger, J.; Rockenberger, J.; Alivisatos, A.P.; Alivisatos, A.P.; van Buuren, T.

    1999-10-01

    We report the observation of size dependent structural disorder by x-ray absorption near-edge spectroscopy (XANES) in InAs and CdSe nanocrystals 17{endash}80thinspthinsp{Angstrom} in diameter. XANES of the In and Cd M{sub 4,5} edges yields features that are sharp for the bulk solid but broaden considerably as the size of the particle decreases. FEFF7 multiple-scattering simulations reproduce the size dependent broadening of the spectra if a bulklike surface reconstruction of a spherical nanocrystal model is included. This illustrates that XANES is sensitive to the structure of the entire nanocrystal including the surface. {copyright} {ital 1999} {ital The American Physical Society }

  19. Analysis of the near-edge X-ray-absorption fine-structure of anthracene: A combined theoretical and experimental study

    SciTech Connect

    Klues, Michael; Witte, Gregor; Hermann, Klaus

    2014-01-07

    The near-edge fine structure of the carbon K-edge absorption spectrum of anthracene was measured and theoretically analyzed by density functional theory calculations implemented in the StoBe code. It is demonstrated that the consideration of electronic relaxation of excited states around localized core holes yields a significant improvement of the calculated excitation energies and reproduces the experimentally observed fine structure well. The detailed analysis of excitation spectra calculated for each symmetry inequivalent excitation center allows in particular to examine the influence of chemical shifts and core hole effects on the excitation energies. Moreover, the visualization of final states explains the large variations in the oscillator strength of various transitions as well as the nature of Rydberg-states that exhibit a notable density of states below the ionization potentials.

  20. X-ray absorption near edge structure study on Acutolysin-C, a zinc-metalloproteinase from Agkistrodon acutus venom: Insight into the acid-inactive mechanism

    NASA Astrophysics Data System (ADS)

    Zhao, Wei; Chu, Wangsheng; Li, Shujun; Liu, Yiwei; Gao, Bin; Niu, Liwen; Teng, Maikun; Benfatto, Maurizio; Hu, Tiandou; Wu, Ziyu

    2007-11-01

    Acutolysin-C, a snake-venom zinc metalloproteinase, displays a distinct pH-dependent proteolytic activity, which has been tentatively assigned to a structural change of the zinc-containing catalytic center. In this work we compare X-ray absorption near-edge structure (XANES) experimental spectra at the Zn K-edge and theoretical calculations of solutions at different pH values. The experimental data show clear differences confirmed by a best fit using the MXAN procedure. The results show that, when pH decreases from pH 8.0 to pH 3.0, the zinc-coordinating catalytic water molecule moves far from the Glu143 residue that is considered to play an essential role in the proteolytic process. Data suggests that this is the possible mechanism that deactivates the metalloproteinase.

  1. Photon-photon absorption and the uniqueness of the spectra of active galactic nuclei

    NASA Technical Reports Server (NTRS)

    Kazanas, D.

    1984-01-01

    The effects of the feedback of e(+)-e(-) pair reinjection in a plasma due to photon-photon absorption of its own radiation was examined. Under the assumption of continuous electron injection with a power law spectrum E to the minus gamma power and Compton losses only, it is shown that for gamma 2 the steady state electron distribution function has a unique form independent of the primary injection spectrum. This electron distribution function can, by synchrotron emission, reproduce the general characteristics of the observed radio to optical active galactic nuclei spectra. Inverse Compton scattering of the synchrotron photons by the same electron distribution can account for their X-ray spectra, and also implies gamma ray emission from these objects. This result is invoked to account for the similarity of these spectra, and it is consistent with observations of the diffuse gamma ray background.

  2. TDDFT prediction of UV-vis absorption and emission spectra of tocopherols in different media.

    PubMed

    Bakhouche, Kahina; Dhaouadi, Zoubeida; Lahmar, Souad; Hammoutène, Dalila

    2015-06-01

    We use the TDDFT/PBE0/6-31+G* method to determine the electronic absorption and emission energies, in different media, of the four forms of tocopherol, which differ by the number and the position of methyl groups on the chromanol. Geometries of the ground state S0 and the first singlet excited state S1 were optimized in the gas phase, and various solvents. The solvent effect is evaluated using an implicit solvation model (IEF-PCM). Our results are compared to the experimental ones obtained for the vitamin E content in several vegetable oils. For all forms of tocopherols, the HOMO-LUMO first vertical excitation is a π-π* transition. Gas phase and non-polar solvents (benzene and toluene) give higher absorption wavelengths than polar solvents (acetone, ethanol, methanol, DMSO, and water); this can be interpreted by a coplanarity between the O-H group and the chroman, allowing a better electronic resonance of the oxygen lone pairs and the aromatic ring, and therefore giving an important absorption wavelength, whereas the polar solvents give high emission wavelengths comparatively to gas phase and non-polar solvents. Fluorescence spectra permit the determination, the separation, and the identification of the four forms of tocopherols by a large difference in emission wavelength values. Graphical Abstract Scheme from process methodological to obtain the absorption and emission spectra for tocopherols.

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

    NASA Technical Reports Server (NTRS)

    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.

  4. Time-resolved Absorption Spectra of the Laser-dressed Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-05-01

    A theoretical study of the transient absorption spectra for the laser-dressed hydrogen atom based on the accurate numerical solution of the time-dependent Schrödinger equation is presented. The timing of absorption is controlled by the time delay between an isolated extreme ultraviolet (XUV) pulse and a dressing infrared (IR) field. We identify two different kinds of physical processes in the spectra. One is the formation of dressed states, signified by the appearance of sidebands between the XUV absorption lines separated by one IR-photon energy. We show that their population is maximized when the XUV pulse coincides with the zero-crossing of the IR field, and that their energy can be manipulated by using a chirped IR field. The other process is the dynamical AC Stark shift induced by the IR field and probed by the XUV pulse. Our calculations indicate that the accidental degeneracy of the hydrogen atom leads to the multiple splittings of each XUV absorption line whose separations change in response to a slowly-varying IR envelope. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 states using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional 3-level model that neglects the dynamical AC Stark effects.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

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

  7. Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Waldo, Geoffrey S.; Carlson, Robert M. K.; Moldowan, J. Michael; Peters, Kenneth E.; Penner-hahn, James E.

    1991-03-01

    The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.

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

    SciTech Connect

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.; Majidi, Hasti; Bunker, Bruce A.; Baxter, Jason B.

    2010-12-03

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

  9. Multiple-scattering approach to the x-ray-absorption spectra of perovskite-type compounds

    NASA Astrophysics Data System (ADS)

    Kitamura, Michihide; Muramatsu, Shinji; Sugiura, Chikara

    1988-04-01

    The metal K x-ray-absorption near-edge structure has been calculated for the first time from a multiple-scattering formalism for the perovskite-type compounds KMnF3, KFeF3, KCoF3, KNiF3, and KZnF3. The calculation includes the effects of a core hole and of Madelung corrections for crystal potentials. It is shown that the results including the lifetime-broadening effect are in good agreement with the experiment of Shulman et al.

  10. Composite Spectra of Broad Absorption Line Quasars in SDSS-III BOSS

    NASA Astrophysics Data System (ADS)

    Herbst, Hanna; Hamann, Fred; Paris, Isabelle; Capellupo, Daniel M.

    2017-01-01

    We present preliminary results from a study of broad absorption line (BAL) quasars in the SDSS-III BOSS survey. We’re particularly interested in BALs because they arise from quasar outflows, which may be a source of feedback to the host galaxy. We analyze median composite spectra for BOSS QSOs in the redshift range 2.1 to 3.4 sorted by the strength of the BAL absorption troughs, parameterized by the Balnicity Index (BI), to study trends in the emission and absorption properties of BAL quasars. The wavelength coverage and high number of quasars observed in the BOSS survey allow us to examine BALs in the Lyman forest. Our main preliminary results when sorting the quasars by BI are 1) doublet absorption lines such as P V 1128A show a 1:1 ratio across all BI, indicating large column densities at all BI. This suggests that weaker BAL troughs result from smaller covering fractions rather than lower column densities. 2) The He II emission line, which is a measure of the far-UV/near-UV hardness of the ionizing continuum, is weaker in the larger BI composite spectra, indicating a far-UV spectral softening correlated with BI. This is consistent with the radiatively-driven BAL outflows being helped by intrinsically weaker ionizing continuum shapes (e.g., Baskin, Laor, and Hamann 2013). We also find a trend for slightly redder continuum slopes in the larger BI composite spectra, suggesting that the slope differences in the near-UV are also intrinsic.

  11. X-ray absorption near-edge structure (XANES) spectroscopy study of the interaction of silver ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli.

    PubMed

    Bovenkamp, Gudrun Lisa; Zanzen, Ulrike; Krishna, Katla Sai; Hormes, Josef; Prange, Alexander

    2013-10-01

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

  12. L-Edge X-ray Absorption Spectroscopy of Dilute Systems Relevant to Metalloproteins Using an X-ray Free-Electron Laser

    PubMed Central

    Mitzner, Rolf; Rehanek, Jens; Kern, Jan; Gul, Sheraz; Hattne, Johan; Taguchi, Taketo; Alonso-Mori, Roberto; Tran, Rosalie; Weniger, Christian; Schröder, Henning; Quevedo, Wilson; Laksmono, Hartawan; Sierra, Raymond G.; Han, Guangye; Lassalle-Kaiser, Benedikt; Koroidov, Sergey; Kubicek, Katharina; Schreck, Simon; Kunnus, Kristjan; Brzhezinskaya, Maria; Firsov, Alexander; Minitti, Michael P.; Turner, Joshua J.; Moeller, Stefan; Sauter, Nicholas K.; Bogan, Michael J.; Nordlund, Dennis; Schlotter, William F.; Messinger, Johannes; Borovik, Andrew; Techert, Simone; de Groot, Frank M. F.; Föhlisch, Alexander; Erko, Alexei; Bergmann, Uwe; Yachandra, Vittal K.; Wernet, Philippe; Yano, Junko

    2013-01-01

    L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming O K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples. PMID:24466387

  13. Electronic structure of individual hybrid colloid particles studied by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the X-ray microscope.

    PubMed

    Henzler, Katja; Guttmann, Peter; Lu, Yan; Polzer, Frank; Schneider, Gerd; Ballauff, Matthias

    2013-02-13

    The electronic structure of individual hybrid particles was studied by nanoscale near-edge X-ray absorption spectromicroscopy. The colloidal particles consist of a solid polystyrene core and a cross-linked poly-N-(isopropylacrylamide) shell with embedded crystalline titanium dioxide (TiO(2)) nanoparticles (d = 6 ± 3 nm). The TiO(2) particles are generated in the carrier network by a sol-gel process at room temperature. The hybrid particles were imaged with photon energy steps of 0.1 eV in their hydrated environment with a cryo transmission X-ray microscope (TXM) at the Ti L(2,3)-edge. By analyzing the image stacks, the obtained near-edge X-ray absorption fine structure (NEXAFS) spectra of our individual hybrid particles show clearly that our synthesis generates TiO(2) in the anastase phase. Additionally, our spectromicroscopy method permits the determination of the density distribution of TiO(2) in single carrier particles. Therefore, NEXAFS spectroscopy combined with TXM presents a unique method to get in-depth insight into the electronic structure of hybrid materials.

  14. Real-time atmospheric absorption spectra for in-flight tuning of an airborne dial system

    NASA Technical Reports Server (NTRS)

    Dombrowski, M.; Walden, H.; Schwemmer, G. K.; Milrod, J.; Korb, C. L.

    1986-01-01

    Real-time measurements of atmospheric absorption spectra are displayed and used to precisely calibrate and fix the frequency of an Alexandrite laser to specific oxygen absorption features for airborne Differential Absorption Lidar (DIAL) measurements of atmospheric pressure and temperature. The DIAL system used contains two narrowband tunable Alexandrite lasers: one is electronically scanned to tune to oxygen absorption features for on-line signals while the second is used to obtain off-line (nonabsorbed) atmospheric return signals. The lidar operator may select the number of shots to be averaged, the altitude, and altitude interval over which the signals are averaged using single key stroke commands. The operator also determines exactly which oxygen absorption lines are scanned by comparing the line spacings and relative strengths with known line parameters, thus calibrating the laser wavelength readout. The system was used successfully to measure the atmospheric pressure profile on the first flights of this lidar, November 20, and December 9, 1985, aboard the NASA Wallops Electra aircraft.

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

    NASA Technical Reports Server (NTRS)

    Gatuzz, E.; Garcia, J.; Menodza, C.; Kallman, T. R.; Witthoeft, M.; Lohfink, A.; Bautista, M. A.; Palmeri, P.; Quinet, P.

    2013-01-01

    We present detailed analyses of oxygen K absorption in the interstellar medium (ISM) using four high-resolution Chandra spectra towards the X-ray low-mass binary XTE J1817-330. The 11-25 A broadband is described with a simple absorption model that takes into account the pileup effect and results in an estimate of the hydrogen column density. The oxygen K-edge region (21-25 A) is fitted with the physical warmabs model, which is based on a photoionization model grid generated with the XSTAR code with the most up-to-date atomic database. This approach allows a benchmark of the atomic data which involves wavelength shifts of both the K lines and photoionization cross sections in order to fit the observed spectra accurately. As a result we obtain: a column density of N(sub H) = 1.38 +/- 0.01 x 10(exp 21) cm(exp -2); ionization parameter of log xi = .2.70 +/- 0.023; oxygen abundance of A(sub O) = 0.689(exp +0.015./-0.010); and ionization fractions of O I/O = 0.911, O II/O = 0.077, and O III/O = 0.012 that are in good agreement with previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse and Sauval (1998), a rescaling with the revision by Asplund et al. (2009) yields A(sub O) = 0.952(exp +0.020/-0.013, a value close to solar that reinforces the new standard. We identify several atomic absorption lines.K-alpha , K-beta, and K-gamma in O I and O II; and K-alpha in O III, O VI, and O VII--last two probably residing in the neighborhood of the source rather than in the ISM. This is the first firm detection of oxygen K resonances with principal quantum numbers n greater than 2 associated to ISM cold absorption.

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

    NASA Technical Reports Server (NTRS)

    Gatuzz, E.; Garcia, J.; Mendoza, C.; Kallman, T. R.; Witthoeft, M.; Lohfink, A.; Bautista, M. A.; Palmeri, P.; Quinet, P.

    2013-01-01

    We present detailed analyses of oxygen K absorption in the interstellar medium (ISM) using four high-resolution Chandra spectra toward the X-ray low-mass binary XTE J1817-330. The 11-25 Angstrom broadband is described with a simple absorption model that takes into account the pile-up effect and results in an estimate of the hydrogen column density. The oxygen K-edge region (21-25 Angstroms) is fitted with the physical warmabs model, which is based on a photoionization model grid generated with the xstar code with the most up-to-date atomic database. This approach allows a benchmark of the atomic data which involves wavelength shifts of both the K lines and photoionization cross sections in order to fit the observed spectra accurately. As a result we obtain a column density of N(sub H) = 1.38 +/- 0.01 × 10(exp 21) cm(exp -2); an ionization parameter of log xi = -2.70 +/- 0.023; an oxygen abundance of A(sub O) = 0.689 (+0.015/-0.010); and ionization fractions of O(sub I)/O = 0.911, O(sub II)/O = 0.077, and O(sub III)/O = 0.012 that are in good agreement with results from previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse & Sauval, a rescaling with the revision by Asplund et al. yields A(sub O) = 0.952(+0.020/-0.013), a value close to solar that reinforces the new standard.We identify several atomic absorption lines-K(alpha), K(beta), and K(gamma) in O(sub I) and O(sub II) and K(alpha) in O(sub III), O(sub VI), and O(sub VII)-the last two probably residing in the neighborhood of the source rather than in the ISM. This is the first firm detection of oxygen K resonances with principal quantum numbers n greater than 2 associated with ISM cold absorption.

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

    SciTech Connect

    Gatuzz, E.; Mendoza, C.; Garcia, J.; Lohfink, A.; Kallman, T. R.; Witthoeft, M.; Bautista, M. A.; Palmeri, P.; Quinet, P. E-mail: claudio@ivic.gob.ve E-mail: alohfink@astro.umd.edu E-mail: michael.c.witthoeft@nasa.gov E-mail: palmeri@umons.ac.be

    2013-05-01

    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 A 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 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 Multiplication-Sign 10{sup 21} cm{sup -2}; an ionization parameter of log {xi} = -2.70 {+-} 0.023; an oxygen abundance of A{sub O}= 0.689{sup +0.015}{sub -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{sub O}=0.952{sup +0.020}{sub -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-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.

  18. Calculation of UV attenuation and colored dissolved organic matter absorption spectra from measurements of ocean color

    NASA Astrophysics Data System (ADS)

    Johannessen, S. C.; Miller, W. L.; Cullen, J. J.

    2003-09-01

    The absorption of ultraviolet and visible radiation by colored or chromophoric dissolved organic matter (CDOM) drives much of marine photochemistry. It also affects the penetration of ultraviolet radiation (UV) into the water column and can confound remote estimates of chlorophyll concentration. Measurements of ocean color from satellites can be used to predict UV attenuation and CDOM absorption spectra from relationships between visible reflectance, UV attenuation, and absorption by CDOM. Samples were taken from the Bering Sea and from the Mid-Atlantic Bight, and water types ranged from turbid, inshore waters to the Gulf Stream. We determined the following relationships between in situ visible radiance reflectance, Lu/Ed (λ) (sr-1), and diffuse attenuation of UV, Kd(λ) (m-1): Kd(323nm) = 0.781[Lu/Ed(412)/Lu/Ed(555)]-1.07; Kd(338nm) = 0.604[Lu/Ed(412)/Lu/Ed(555)]-1.12; Kd(380 nm) = 0.302[Lu/Ed(412)/Lu/Ed(555)]-1.24. Consistent with published observations, these empirical relationships predict that the spectral slope coefficient of CDOM absorption increases as diffuse attenuation of UV decreases. Excluding samples from turbid bays, the ratio of the CDOM absorption coefficient to Kd is 0.90 at 323 nm, 0.86 at 338 nm, and 0.97 at 380 nm. We applied these relationships to SeaWiFS images of normalized water-leaving radiance to calculate the CDOM absorption and UV attenuation in the Mid-Atlantic Bight in May, July, and August 1998. The images showed a decrease in UV attenuation from May to August of approximately 50%. We also produced images of the areal distribution of the spectral slope coefficient of CDOM absorption in the Georgia Bight. The spectral slope coefficient increased offshore and changed with season.

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

    USGS Publications Warehouse

    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

  20. The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix

  1. Chemical shifts of K-X-ray absorption edges on copper in different compounds by X-ray absorption spectroscopy (XAS) with Synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Joseph, D.; Basu, S.; Jha, S. N.; Bhattacharyya, D.

    2012-03-01

    Cu K X-ray absorption edges were measured in compounds such as CuO, Cu(CH3CO2)2, Cu(CO3)2, and CuSO4 where Cu is present in oxidation state of 2+, using the energy dispersive EXAFS beamline at INDUS-2 Synchrotron radiation source at RRCAT, Indore. Energy shifts of ˜4-7 eV were observed for Cu K X-ray absorption edge in the above compounds compared to its value in elemental copper. The difference in the Cu K edge energy shifts in the different compounds having same oxidation state of Cu shows the effect of different chemical environments surrounding the cation in the above compounds. The above chemical effect has been quantitatively described by determining the effective charges on Cu cations in the above compounds.

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

    SciTech Connect

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

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

  3. Infrared band absorptance correlations and applications to nongray radiation. [mathematical models of absorption spectra for nongray atmospheres in order to study air pollution

    NASA Technical Reports Server (NTRS)

    Tiwari, S. N.; Manian, S. V. S.

    1976-01-01

    Various mathematical models for infrared radiation absorption spectra for atmospheric gases are reviewed, and continuous correlations for the total absorptance of a wide band are presented. Different band absorptance correlations were employed in two physically realistic problems (radiative transfer in gases with internal heat source, and heat transfer in laminar flow of absorbing-emitting gases between parallel plates) to study their influence on final radiative transfer results. This information will be applied to the study of atmospheric pollutants by infrared radiation measurement.

  4. The effect of ionization on the infrared absorption spectra of PAHs: A preliminary report

    NASA Technical Reports Server (NTRS)

    Defrees, Doug J.; Miller, M. D.

    1989-01-01

    The emission lines observed in many interstellar IR sources at 3.28, 6.2, 7.7, 8.7, and 11.3 microns are theorized to originate from polycyclic aromatic hydrocarbons (PAHs). These assignments are based on analyses of lab IR spectra of neutral PAHs. However, it is likely that in the interstellar medium that PAHs are ionized, i.e., are positively charged. Besides, as pointed out by Allamandola et al., although the IR emission band spectrum resembles what one might expect from a mixture of PAHs, it does not match in details such as frequency, band profile, or relative intensities predicted from the absorption spectra of any known PAH molecule. One source of more information to test the PAH theory is ab initio molecular orbital theory. It can be used to compute, from first principles, the geometries, vibrational frequencies, and vibrational intensities for model PAH compounds which are difficult to study in the lab. The Gaussian 86 computer program was used to determine the effect of ionization on the infrared absorption spectra of several small PAHs: naphthalene and anthracene. A preliminary report is presented of the results of these calculations.

  5. Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: Comparison between experiment and theory

    NASA Astrophysics Data System (ADS)

    Bravo, IváN.; Aranda, Alfonso; Hurley, Michael D.; Marston, George; Nutt, David R.; Shine, Keith P.; Smith, Kevin; Wallington, Timothy J.

    2010-12-01

    Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.

  6. Effect of solvent on absorption spectra of all-trans-{beta}-carotene under high pressure

    SciTech Connect

    Liu, W. L.; Zheng, Z. R.; Liu, Z. G.; Zhu, R. B.; Wu, W. Z.; Li, A. H.; Yang, Y. Q.; Dai, Z. F.; Su, W. H.

    2008-03-28

    The absorption spectra of all-trans-{beta}-carotene in n-hexane and carbon disulfide (CS{sub 2}) solutions are measured under high pressure at ambient temperature. The common redshift and broadening in the spectra are observed. Simulation of the absorption spectra was performed by using the time-domain formula of the stochastic model. The pressure dependence of the 0-0 band wavenumber is in agreement with the Bayliss theory at pressure higher than 0.2 GPa. The deviation of the linearity at lower pressure is ascribed to the reorientation of the solvent molecules. Both the redshift and broadening are stronger in CS{sub 2} than that in n-hexane because of the more sensitive pressure dependence of dispersive interactions in CS{sub 2} solution. The effect of pressure on the transition moment is explained with the aid of a simple model involving the relative dimension, location, and orientation of the solute and solvent molecules. The implication of these results for light-harvesting functions of carotenoids in photosynthesis is also discussed.

  7. Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

    SciTech Connect

    Liu, Xiang; Cui, Shengsheng; Sun, Zijun; Ren, Yang; Zhang, Xiaoyi; Du, Pingwu

    2016-01-21

    Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onset potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.

  8. Effects of Spectralon absorption on reflectance spectra of typical planetary surface analog materials.

    PubMed

    Zhang, Hao; Yang, Yazhou; Jin, Weidong; Liu, Chujian; Hsu, Weibiao

    2014-09-08

    Acquiring accurate visible and near-infrared (VisNIR) reflectance values of atmosphereless celestial bodies is very important in inferring the physical and geological properties of their surficial materials. When a calibration target with inherent non-trivial absorption features is used, the calibrated reflectance would essentially always contain spurious spectral features and the spectroscopic data may easily be misinterpreted if the artifact is not properly taken care of. We demonstrate with laboratory reflectance measurements that the VisNIR spectra of three typical planetary surface analog materials, lunar simulant JSC-1A, olivine and pyroxene grains, have an artificial peak at 2.1 µm when Spectralon-type plaque made of polytetrafluoroethylene is used as the calibration target in the NIR region. The degree of severity of this artifact is dependent on the strength of the 2.0 µm absorption feature of the mineral. Empirical methods are proposed to remove this artifact to bring the spectra close to that calibrated by a gold mirror which does not have any conspicuous absorption features in the NIR region. The correction methods may be applied to reflectance data acquired by the VisNIR imaging spectrometer onboard the Yutu Rover of the Chinese Chang'E 3 lunar mission which employed an onboard Spectralon-type calibration target.

  9. Comparison between IR absorption and raman scattering spectra of liquid and supercritical 1-butanol.

    PubMed

    Sokolova, Maia; Barlow, Stephen J; Bondarenko, Galina V; Gorbaty, Yuri E; Poliakoff, Martyn

    2006-03-23

    Raman spectra of 1-butanol have been obtained at a constant pressure of 500 bar up to 350 degrees C and along isotherms 250, 300, and 350 degrees C up to 600 bar. The purpose of the experiment was to compare responses of Raman and IR absorption spectroscopy to the forming of O-H...O bonds in alcohols. As a result, some important inferences were drawn from the experiment. In particular, it has been estimated quantitatively how the intensity of Raman scattering in the region of the OH band depends on the extent of hydrogen bonding. As might be expected, the dependence is much weaker than in the case of the IR absorption. As was shown, the ratio of integrated intensities of bonded molecules in the absorption and scattering spectra is a constant and does not depend on temperature and density. The effect of cooperativity of hydrogen bonds is confirmed. It was also found that even at high pressures, a noticeable amount of nonbonded molecules exists at room temperature.

  10. BRIEF COMMUNICATION: Calculation of a magnetic field effect on emission spectra of light diatomic molecules for diagnostic application to fusion edge plasmas

    NASA Astrophysics Data System (ADS)

    Shikama, T.; Fujii, K.; Mizushiri, K.; Hasuo, M.; Kado, S.; Zushi, H.

    2009-12-01

    A scheme for computation of emission spectra of light diatomic molecules under external magnetic and electric fields is presented. As model species in fusion edge plasmas, the scheme is applied to polarization-resolved emission spectra of H2, CH, C2, BH and BeH molecules. The possibility of performing spatially resolved measurements of these spectra is examined.

  11. A combined DFT and restricted open-shell configuration interaction method including spin-orbit coupling: Application to transition metal L-edge X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Roemelt, Michael; Maganas, Dimitrios; DeBeer, Serena; Neese, Frank

    2013-05-01

    A novel restricted-open-shell configuration interaction with singles (ROCIS) approach for the calculation of transition metal L-edge X-ray absorption spectra is introduced. In this method, one first calculates the ground state and a number of excited states of the non-relativistic Hamiltonian. By construction, the total spin is a good quantum number in each of these states. For a ground state with total spin S excited states with spin S' = S, S - 1, and S + 1 are constructed. Using Wigner-Eckart algebra, all magnetic sublevels with MS = S, …, -S for each multiplet of spin S are obtained. The spin-orbit operator is represented by a mean-field approximation to the full Breit-Pauli spin-orbit operator and is diagonalized over this N-particle basis. This is equivalent to a quasi-degenerate treatment of the spin-orbit interaction to all orders. Importantly, the excitation space spans all of the molecular multiplets that arise from the atomic Russell-Saunders terms. Hence, the method represents a rigorous first-principles approach to the complicated low-symmetry molecular multiplet problem met in L-edge X-ray absorption spectroscopy. In order to gain computational efficiency, as well as additional accuracy, the excitation space is restricted to single excitations and the configuration interaction matrix is slightly parameterized in order to account for dynamic correlation effects in an average way. To this end, it is advantageous to employ Kohn-Sham rather than Hartree-Fock orbitals thus defining the density functional theory/ROCIS method. However, the method can also be used in an entirely non-empirical fashion. Only three global empirical parameters are introduced and have been determined here for future application of the method to any system containing any transition metal. The three parameters were carefully calibrated using the L-edge X-ray absorption spectroscopy spectra of a test set of coordination complexes containing first row transition metals. These

  12. First-principles calculation of ground and excited-state absorption spectra of ruby and alexandrite considering lattice relaxation

    NASA Astrophysics Data System (ADS)

    Watanabe, Shinta; Sasaki, Tomomi; Taniguchi, Rie; Ishii, Takugo; Ogasawara, Kazuyoshi

    2009-02-01

    We performed first-principles calculations of multiplet structures and the corresponding ground-state absorption and excited-state absorption spectra for ruby (Cr3+:α-Al2O3) and alexandrite (Cr3+:BeAl2O4) which included lattice relaxation. The lattice relaxation was estimated using the first-principles total energy and molecular-dynamics method of the CASTEP code. The multiplet structure and absorption spectra were calculated using the configuration-interaction method based on density-functional calculations. For both ruby and alexandrite, the theoretical absorption spectra, which were already in reasonable agreement with experimental spectra, were further improved by consideration of lattice relaxation. In the case of ruby, the peak positions and peak intensities were improved through the use of models with relaxations of 11 or more atoms. For alexandrite, the polarization dependence of the U band was significantly improved, even by a model with a relaxation of only seven atoms.

  13. Theoretical studies on the vibrationally-resolved absorption and fluorescence spectra of H-Pyrene+ and H-Coronene+

    NASA Astrophysics Data System (ADS)

    Li, JunFeng; Tian, GuanJun; Luo, Yi; Cao, ZeXing

    2015-11-01

    H-Pyrene+ and H-Coronene+ are important carrier candidates for the diffuse interstellar band. In order to understand the observed absorption and fluorescence emission spectra of H-Pyrene+ and H-Coronene+, time-dependent density functional theory (TD-DFT) method and Franck-Condon approximation have been employed to simulate the corresponding vibrationally-resolved optical spectra. For H-Pyrene+, the calculated absorption, emission and 0-0 band energies are in good agreement with the experimental values. The strong absorption and emission vibrational peaks near the 0-0 band match well with the experiment peaks. A noticeable deviation for several weak peaks far away from the origin band is observed, as a result of the vibronic coupling with other excited states. For H-Coronene+, the predicted vibrationally resolved electronic absorption and emission spectra resemble very well their experimental counterparts spectra, allowing to fully assign the observed vibronic peaks.

  14. Simulations of X-ray absorption spectra: the effect of the solvent.

    PubMed

    Penfold, Thomas J; Curchod, Basile F E; Tavernelli, Ivano; Abela, Rafael; Rothlisberger, Ursula; Chergui, Majed

    2012-07-14

    We perform quantum mechanics/molecular mechanics molecular dynamics simulations on the [Pt(2)(P(2)O(5)H(2))(4)](4-) (abbreviated PtPOP) complex; in water, dimethylformamide and ethanol. These are used to calculate the ground state X-ray absorption spectrum of the complex. The structural parameters from X-ray spectra are usually extracted using a fit of the experimental data. In such simulations the solvent is neglected meaning that any effect of the local environment will be compensated for by structural changes of the solute, leading to possible discrepancies in the extracted structural parameters. Our simulations show a significant solvent effect on the spectra, which has important implications for the structural analysis of molecules in solution.

  15. Ultrafast optical nonlinearity, electronic absorption, vibrational spectra and solvent effect studies of ninhydrin.

    PubMed

    Sajan, D; Devi, T Uma; Safakath, K; Philip, Reji; Němec, Ivan; Karabacak, M

    2013-05-15

    FT-IR, FT-Raman and UV-Vis spectra of the nonlinear optical molecule ninhydrin have been recorded and analyzed. The equilibrium geometry, bonding features, and harmonic vibrational wavenumbers have been investigated with the help of B3LYP density functional theory method. A detailed interpretation of the vibrational spectra is carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology. Solvent effects have been calculated using time-dependent density functional theory in combination with the polarized continuum model. Natural bond orbital analysis confirms the occurrence of strong intermolecular hydrogen bonding in the molecule. Employing the open-aperture z-scan technique, nonlinear optical absorption of the sample has been studied in the ultrafast and short-pulse excitation regimes, using 100 fs and 5 ns laser pulses respectively. It is found that ninhydrin exhibits optical limiting for both excitations, indicating potential photonic applications.

  16. Solvatochromic behavior of the electronic absorption spectra of gallic acid and some of its azo derivatives

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Hagagg, Sawsan S.; Ali, Alaa E.; Nasr, Nessma M.

    The electronic absorption spectra of gallic acid and its azo derivatives have been studied in various solvents of different polarities. Multiple regression techniques were applied to calculate the regression and correlation coefficients based on an equation that relates the wavenumbers of the absorption band maxima (υmax-) to the solvent parameters; refractive index (n), dielectric constant (D), empirical Kamlet-Taft solvent parameters, π*(dipolarity/polarizability), α (solvent hydrogen-bond donor acidity) and β (solvent hydrogen-bond acceptor basicity). The fitting coefficient obtained from this analysis allows estimating the contribution of each type of interactions relative to total spectral shifts in solution. The dependence of υmax- on the solvent parameters indicates that the obtained bands are affected by specific and non-specific solute-solvent interactions.

  17. Paradoxical solvent effects on the absorption and emission spectra of amino-substituted perylene monoimides.

    PubMed

    Zoon, Peter D; Brouwer, Albert M

    2005-08-12

    In N-(2,5-di-tert-butylphenyl)-9-pyrrolidinoperylene-3,4-dicarboximide (5PI) the absorption and emission spectra display large solvatochromic shifts, but, remarkably, the Stokes shift is practically independent of solvent polarity. This unique behavior is caused by the extraordinarily large ground-state dipole moment of 5PI, which further increases upon increasing the solvent polarity, whereas the excited-state dipole moment is less solvent dependent. In the corresponding piperidine compound, 6PI, this effect is much less important owing to the weaker coupling between the amino group and the aromatic imide moiety, and in the corresponding naphthalimide, 5NI, it is absent. The latter shows the conventional solvatochromic behavior of a push-pull substituted conjugated system, that is, minor shifts in absorption and a larger change in the emission energy with solvent polarity.

  18. The X-shooter sample of GRB afterglow spectra: Properties of the absorption features

    NASA Astrophysics Data System (ADS)

    de Ugarte Postigo, Antonio

    2015-08-01

    Since its commissioning at ESO's Very Large Telescope in 2009, the X-shooter spectrograph has become the reference instrument in gamma-ray burst (GRB) afterglow spectroscopy. During this time our collaboration has collected more than 70 spectra of GRB afterglows, with redshifts ranging from 0.06 to 6.3. Thanks to their extreme luminosity and simple intrinsic shape, GRB spectra are optimal tools for the study of galactic environments at basically any redshift. Being produced by the death of short-lived massive stars, they are also tracers of star formation.I will present the sample of absorption spectral features identified in X-shooter's GRB spectra describing observation and analysis techniques. The different features are compared with the characteristics of the explosion (duration, spectral shape, energetics, etc.) and with the properties of the host galaxy (mass, age, etc.) to improve our understanding of the nature of the explosions and how they interact with their environments. Using the large redshift range of the spectra collection we perform studies of the evolution of GRB environments across the history of the Universe and their relation with the evolution of star formation.

  19. Gain and Absorption Spectra of Quantum Wire Lasers Diodes Grown on Nonplanar Substrates

    DTIC Science & Technology

    1992-04-01

    SIMMJ^ COMPONENT PART NOTICE THIS PAPER IS A COMPONENT PART OF THE FOLLOWING COMPILATION REPORT: TTT1F: Integrated Photonics Research. Volume 10...i’t’y Co" .,.*» Dist kl Avji. :.;;fl,’or Spital ulll’MAR85Mb:> OPI: DTIC-TID Integrated Photonics Research -1 Gain and Absorption Spectra of...modulators and switches. 92-31749 Integrated Photonics Research 59 MC2-2 References: 1. E. Kapon, D.M. Hwang and R. Bhat, Phys. Rev. Lett. 63, 430 (1989

  20. Quantum-chemical investigation of the structure and electronic absorption spectra of electroluminescent zinc complexes

    NASA Astrophysics Data System (ADS)

    Minaev, B. F.; Baryshnikov, G. V.; Korop, A. A.; Minaeva, V. A.; Kaplunov, M. G.

    2013-01-01

    Using the quantum chemical methods of the density functional theory and of the electron density topological analysis, we have studied the structure of two recently synthesized electroluminescent zinc complexes, one with aminoquinoline ligands and the other with a Schiff base (N,O-donor). The energies and intensities of vertical excitations for the molecules under study have been calculated in terms of the PM3 semiempirical approximation taking into account the configurational interaction between singly excited singlet excited states. Good agreement between calculation results and experimental data on the electron density topological characteristics and on the visible and UV absorption spectra has been obtained.

  1. Solvent effects on the electronic absorption spectra and acid strength of some substituted pyridinols

    NASA Astrophysics Data System (ADS)

    Hashem, Elham Y.; Saleh, Magda S.

    2002-01-01

    The electronic absorption spectra of some substituted pyridinols in organic solvents of different polarities are studied. Also, the solvent effects on the intramolecular charge transfer bands are discussed using various solvent parameters. The acid-base equilibria of the compounds used are studied spectrophotometrically in various mixed aqueous solvents at 25 °C and 0.1 M ionic strength (NaClO 4). Furthermore, the influence of the solvents on the dissociation constants and tautomeric equilibria of a pyridinol derivatives are discussed. The effect of molecular structure of the pyridinols on the p K's is also examined.

  2. IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

    NASA Astrophysics Data System (ADS)

    Strekal', N. D.; Motevich, I. G.; Nowicky, J. W.; Maskevich, S. A.

    2007-01-01

    We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering.

  3. A Survey for Intervening CIV Absorption-Line Systems Using SDSS Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Monier, Eric M.; Nestor, D. B.; Daino, M. M.; Quider, A. M.; Rao, S. M.; Turnshek, D. A.

    2006-06-01

    Intervening CIV absorption-line systems are readily found in Sloan Digital Sky Survey (SDSS) quasar spectra at redshifts z > 1.5. Given the large number of absorbers, high statistical accuracy is possible in comparison to what was possible in the past. Here we present preliminary results on the incidence and evolution of the CIV systems as a function of CIV rest equivalent width. The absorber incidence is proportional to the product of gas cross-section and co-moving number density of absorbers, while the rest equivalent width is related to their kinematic spread. We discuss the interpretation of our results.

  4. Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

    2009-11-01

    In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

  5. The energy calibration of x-ray absorption spectra using multiple-beam diffraction

    SciTech Connect

    Hagelstein, M.; Cunis, S. ); Frahm, R. ); Rabe, P. )

    1992-01-01

    A new method for calibrating the energy scale of x-ray absorption spectra from an energy dispersive spectrometer has been developed. Distinct features in the diffracted intensity of the curved silicon crystal monochromator have been assigned to multiple-beam diffraction. The photon energies of these structures can be calculated if the precise spacing of the diffracting planes and the orientation of the crystal relative to the incident synchrotron radiation are known. The evaluation of Miller indices of operative reflections and the calculation of the corresponding photon energy is presented. The assignment of operative reflexes is simplified if the monochromator crystal can be rotated around the main diffracting vector {bold H}.

  6. Resonant Photoemission and M_{2,3}-Absorption Spectra in Nickel Dichloride

    NASA Astrophysics Data System (ADS)

    Igarashi, J.

    Ni 3p-resonant photoemission and Ni M_{2,3}-absorption spectra are calculated in detail on a cluster of (NiCl_6)^{4-} with the use of the transition matrix elements evaluated on the Herman-Skillman potential in Ni atom. Overall spectral shape agrees well with experiment, allowing a determination of the parameters which characterize Ni 3d and Cl 3p states. Resonance behavior is discussed near the Ni 3p-core level photothreshold. The resonant enhancement is found to be larger for the peak with higher binding energy in the d^7-multiplets.

  7. Absorption and resonance Raman spectra of Pb2, Pb3 and Pb4 in xenon matrices

    NASA Technical Reports Server (NTRS)

    Stranz, D. D.; Khanna, R. K.

    1980-01-01

    Lead metal was vaporized and trapped in solid xenon at 12K. Electronic absorption and resonance Raman spectra were recorded of the resulting matrix, which was shown to contain Pb2, Pb3, and possibly Pb4 molecular species. The vibrational frequency for Pb2 is determined to be 108/cm for the ground state, with a dissociation energy of 82000/cm. Ad3h symmetry is indicated for the Pb3 species, with nu sub 1=117/cm and nu sub 2 = 96 /cm. The existence of Pb4 is suggested by a fundamental and overtone of 111/cm spacing.

  8. A ubiquitous absorption feature in the X-ray spectra of BL Lacertae objects

    NASA Technical Reports Server (NTRS)

    Madejski, Greg M.; Mushotzky, Richard F.; Weaver, Kimberly A.; Arnaud, Keith A.; Urry, C. Megan

    1991-01-01

    The paper presents the broadband (0.5-20-keV) X-ray spectra of five X-ray bright BL Lac objects observed with the Einstein Observatory Solid State Spectrometer (SSS) and Monitor Proportional Counter (MPC) detectors. The combination of moderate energy resolution and broad spectral coverage makes it possible to confirm the presence of an absorption feature at an energy of 650 eV in the BL Lac object PKS 2155-304, originally reported by Canizares and Kruper (1984) based on higher resolution Einstein Objective Grating Spectrometer (OGS) data.

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

    SciTech Connect

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

    1997-05-01

    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, {delta}H of the Josephson lines was found to vary linearly with P{sup 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} {ital 1997} {ital The American Physical Society}

  10. The Intervening Galaxies Hypothesis of the Absorption Spectra of Quasi-Stellar Objects: Some Statistical Studies

    NASA Astrophysics Data System (ADS)

    Duari, Debiprosad; Narlikar, Jayant V.

    This paper examines, in the light of the available data, the hypothesis that the heavy element absorption line systems in the spectra of QSOs originate through en-route absorption by intervening galaxies, halos etc. Several statistical tests are applied in two different ways to compare the predictions of the intervening galaxies hypothesis (IGH) with actual observations. The database is taken from a recent 1991 compilation of absorption line systems by Junkkarinen, Hewitt and Burbidge. Although, prima facie, a considerable gap is found between the predictions of the intervening galaxies hypothesis and the actual observations despite inclusion of any effects of clustering and some likely selection effects, the gap narrows after invoking evolution in the number density of absorbers and allowing for the incompleteness and inhomogeneity of samples examined. On the latter count the gap might be bridgeable by stretching the parameters of the theory. It is concluded that although the intervening galaxies hypothesis is a possible natural explanation to account for the absorption line systems and may in fact do so in several cases, it seems too simplistic to be able to account for all the available data. It is further stressed that the statistical techniques described here will be useful for future studies of complete and homogenous samples with a view to deciding the extent of applicability of the IGH.

  11. Galactic Soft X-ray Emission Revealed with Spectroscopic Study of Absorption and Emission Spectra

    NASA Astrophysics Data System (ADS)

    Yamasaki, Noriko Y.; Mitsuda, K.; Takei, Y.; Hagihara, T.; Yoshino, T.; Wang, Q. D.; Yao, Y.; McCammon, D.

    2010-03-01

    Spectroscopic study of Oxygen emission/absorption lines is a new tool to investigate the nature of the soft X-ray background. We investigated the emission spectra of 14 fields obtained by Suzaku, and detected OVII and OVIII lines separately. There is an almost isotropic OVII line emission with 2 LU intensity. As the attenuation length in the Galactic plane for that energy is short, that OVII emission should arise within 300 pc of our neighborhood. In comparison with the estimated emission measure for the local bubble, the most plausible origin of this component is the solar wind charge exchange with local interstellar materials. Another component presented from the correlation between the OVII and OVIII line intensity is a thermal emission with an apparent temperature of 0.2 keV with a field-to-field fluctuation of 10% in temperature, while the intensity varies about a factor of 4. By the combination analysis of the emission and the absorption spectra, we can investigate the density and the scale length of intervening plasma separately. We analyzed the Chanrdra grating spectra of LMC X-3 and PKS 2155-304, and emission spectra toward the line of sight by Suzaku. In both cases, the combined analysis showed that the hot plasma is not iso-thermal nor uniform. Assuming an exponential disk distribution, the thickness of the disk is as large as a few kpc. It suggests that there is a thick hot disk or hot halo surrounding our Galaxy, which is similar to X-ray hot haloes around several spiral galaxies.

  12. Determination of phosphorus using high-resolution diphosphorus molecular absorption spectra produced in the graphite furnace

    NASA Astrophysics Data System (ADS)

    Huang, Mao Dong; Becker-Ross, Helmut; Okruss, Michael; Geisler, Sebastian; Florek, Stefan

    2016-01-01

    Molecular absorption of diphosphorus was produced in a graphite furnace and evaluated in view of its suitability for phosphorus determination. Measurements were performed with two different high-resolution continuum source absorption spectrometers. The first system is a newly in-house developed simultaneous broad-range spectrograph, which was mainly used for recording overview absorption spectra of P2 between 193 nm and 245 nm. The region covers the main part of the C 1Σu+ ← X 1Σg+ electronic transition and shows a complex structure with many vibrational bands, each consisting of a multitude of sharp rotational lines. With the help of molecular data available for P2, an assignment of the vibrational bands was possible and the rotational structure could be compared with simulated spectra. The second system is a commercial sequential continuum source spectrometer, which was used for the basic analytical measurements. The P2 rotational line at 204.205 nm was selected and systematically evaluated with regard to phosphorus determination. The conditions for P2 generation were optimized and it was found that the combination of a ZrC modified graphite tube and borate as a chemical modifier were essential for a good production of P2. Serious interferences were found in the case of nitrate and sulfuric acid, although the nitrate interference can be eliminated by a higher pyrolysis temperature. The reliability of the method was proved by analysis of certified samples. Using standard tubes, a characteristic mass of 10 ng and a limit of detection of 7 ng were found. The values could further be improved by a factor of ten using a miniaturized tube with an internal diameter of 2 mm. Compared to the conventional method based on the phosphorus absorption line at 213.618 nm, the advantages of using P2 are the gentle temperature conditions and the potential of performing a simultaneous multi-line evaluation to further improve the limit of detection.

  13. Spectral estimation of plasma fluctuations. II. Nonstationary analysis of edge localized mode spectra

    SciTech Connect

    Riedel, K.S.; Sidorenko, A. ); Bretz, N. ); Thomson, D.J. )

    1994-03-01

    Several analysis methods for nonstationary fluctuations are described and applied to the edge localized mode (ELM) instabilities of limiter H-mode plasmas. The microwave scattering diagnostic observes poloidal [ital k][sub [theta

  14. Radiation effects in water ice: a near-edge x-ray absorption fine structure study.

    PubMed

    Laffon, C; Lacombe, S; Bournel, F; Parent, Ph

    2006-11-28

    The changes in the structure and composition of vapor-deposited ice films irradiated at 20 K with soft x-ray photons (3-900 eV) and their subsequent evolution with temperatures between 20 and 150 K have been investigated by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K edge. We observe the hydroxyl OH, the atomic oxygen O, and the hydroperoxyl HO(2) radicals, as well as the oxygen O(2) and hydrogen peroxide H(2)O(2) molecules in irradiated porous amorphous solid water (p-ASW) and crystalline (I(cryst)) ice films. The evolution of their concentrations with the temperature indicates that HO(2), O(2), and H(2)O(2) result from a simple step reaction fuelled by OH, where O(2) is a product of HO(2) and HO(2) a product of H(2)O(2). The local order of ice is also modified, whatever the initial structure is. The crystalline ice I(cryst) becomes amorphous. The high-density amorphous phase (I(a)h) of ice is observed after irradiation of the p-ASW film, whose initial structure is the normal low-density form of the amorphous ice (I(a)l). The phase I(a)h is thus peculiar to irradiated ice and does not exist in the as-deposited ice films. A new "very high density" amorphous phase-we call I(a)vh-is obtained after warming at 50 K the irradiated p-ASW ice. This phase is stable up to 90 K and partially transforms into crystalline ice at 150 K.

  15. Probing the electronic and geometric structure of ferric and ferrous myoglobins in physiological solutions by Fe K-edge absorption spectroscopy.

    PubMed

    Lima, Frederico A; Penfold, Thomas J; van der Veen, Renske M; Reinhard, Marco; Abela, Rafael; Tavernelli, Ivano; Rothlisberger, Ursula; Benfatto, Maurizio; Milne, Christopher J; Chergui, Majed

    2014-01-28

    We present an iron K-edge X-ray absorption study of carboxymyoglobin (MbCO), nitrosylmyoglobin (MbNO), oxymyoglobin (MbO2), cyanomyoglobin (MbCN), aquomet myoglobin (metMb) and unligated myoglobin (deoxyMb) in physiological media. The analysis of the XANES region is performed using the full-multiple scattering formalism, implemented within the MXAN package. This reveals trends within the heme structure, absent from previous crystallographic and X-ray absorption analysis. In particular, the iron-nitrogen bond lengths in the porphyrin ring converge to a common value of about 2 Å, except for deoxyMb whose bigger value is due to the doming of the heme. The trends of the Fe-Nε (His93) bond length is found to be consistent with the effect of ligand binding to the iron, with the exception of MbNO, which is explained in terms of the repulsive trans effect. We derive a high resolution description of the relative geometry of the ligands with respect to the heme and quantify the magnitude of the heme doming in the deoxyMb form. Finally, time-dependent density functional theory is used to simulate the pre-edge spectra and is found to be in good agreement with the experiment. The XAS spectra typically exhibit one pre-edge feature which arises from transitions into the unoccupied dσ and dπ - πligand* orbitals. 1s → dπ transitions contribute weakly for MbO2, metMb and deoxyMb. However, despite this strong Fe d contribution these transitions are found to be dominated by the dipole (1s → 4p) moment due to the low symmetry of the heme environment.

  16. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules

    SciTech Connect

    Kolczewski, C.; Puettner, R.; Martins, M.; Schlachter, A.S.; Snell, G.; Sant'Anna, M.M.; Hermann, K.; Kaindl, G.

    2006-01-21

    We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.

  17. Geometric Structure Determination of N694C Lipoxygenase: a Comparative Near-Edge X-Ray Absorption Spectroscopy And Extended X-Ray Absorption Fine Structure Study

    SciTech Connect

    Sarangi, R.; Hocking, R.K.; Neidig, M.L.; Benfatto, M.; Holman, T.R.; Solomon, E.I.; Hodgson, K.O.; Hedman, B.

    2009-05-27

    The mononuclear nonheme iron active site of N694C soybean lipoxygenase (sLO1) has been investigated in the resting ferrous form using a combination of Fe-K-pre-edge, near-edge (using the minuit X-ray absorption near-edge full multiple-scattering approach), and extended X-ray absorption fine structure (EXAFS) methods. The results indicate that the active site is six-coordinate (6C) with a large perturbation in the first-shell bond distances in comparison to the more ordered octahedral site in wild-type sLO1. Upon mutation of the asparigine to cystiene, the short Fe-O interaction with asparigine is replaced by a weak Fe-(H{sub 2}O), which leads to a distorted 6C site with an effective 5C ligand field. In addition, it is shown that near-edge multiple scattering analysis can give important three-dimensional structural information, which usually cannot be accessed using EXAFS analysis. It is further shown that, relative to EXAFS, near-edge analysis is more sensitive to partial coordination numbers and can be potentially used as a tool for structure determination in a mixture of chemical species.

  18. Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

    NASA Astrophysics Data System (ADS)

    Ai, Yuejie; Tian, Guangjun; Luo, Yi

    2013-07-01

    Two-photon absorption spectra of green fluorescent proteins (GFPs) often show a blue-shift band compared to their conventional one-photon absorption spectra, which is an intriguing feature that has not been well understood. We present here a systematic study on one- and two-photon spectra of GFP chromophore by means of the density functional response theory and complete active space self-consistent field (CASSCF) methods. It shows that the popular density functional fails to provide correct vibrational progression for the spectra. The non-Condon vibronic coupling, through the localised intrinsic vibrational modes of the chromophore, is responsible for the blue-shift in the TPA spectra. The cis to trans isomerisation can be identified in high-resolution TPA spectra. Our calculations demonstrate that the high level ab initio multiconfigurational CASSCF method, rather than the conventional density functional theory is required for investigating the essential excited-state properties of the GFP chromophore.

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

    ERIC Educational Resources Information Center

    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…

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

    SciTech Connect

    Alkire, Randall W.

    2016-11-01

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

  1. Absorption in X-ray spectra of high-redshift quasars

    NASA Technical Reports Server (NTRS)

    Elvis, Martin; Fiore, Fabrizio; Wilkes, Belinda; Mcdowell, Jonathan; Bechtold, Jill

    1994-01-01

    We present evidence that X-ray absorption is common in high-redshift quasars. We have studied six high-redshift (z approximately 3) quasars with the ROSAT Position Sensitive Proportional Counter (PSPC) of which four are in directions of low Galactic N(sub H). Three out of these four show excess absorption, while only three in approximately 50 z approximately less than 0.4 quasars do, indicating that such absorption must be common, but not ubiquitous, at high redshifts, and that the absorbers must lie at z greater than 0.4. The six quasars were: S5 0014+81, Q0420-388, PKS 0438-436, S4 0636+680. PKS 2000-330, PKS 2126-158, which have redshifts between 2.85 and 3.78. PKS 0438-436 and PKS 2126-158 show evidence for absorption above the local Galactic value at better than 99.999% confidence level. If the absorber is at the redshift of the quasar, then values of N(sub H) = (0.86(+0.49, -0.28)) x 10(exp 22) atoms/sq cm for PKS 0438-436, and N(sub H) = (1.45(+1.20, -0.64)) x 10(exp 22) atoms/ sq cm for PKS 2126-158, are implied, assuming solar abundances. The spectrum of S4 0636+680 also suggests the presence of a similarly large absorption column density at the 98% confidence level. This absorption reverses the trend for the most luminous active galactic nuclei (AGN) to have the least X-ray absorption, so a new mechanism is likely to be responsible. Intervening absorption due to damped Lyman(alpha) systems is a plausible cause. We also suggest, as an intrinsic model, that intracluster material, e.g., a cooling flow, around the quasar could account for both the X-ray spectrum and other properties of these quasars. All the quasars are radio-loud and three are gigahertz peaked (two of the three showing absorption). No excess absorption above the Galactic value is seen toward Q0420-388. This quasar has two damped Lyman(alpha) systems at z = 3.08. The limit on the X-ray column density implies a low ionization fraction, N(H I)/N(H) approximately greater than 4 x 10(exp -3) (3

  2. Removal of Mars atmospheric gas absorption from Phobos-2/ISM spectra

    NASA Astrophysics Data System (ADS)

    Castronuovo, M. M.; Ulivieri, C.

    Infrared imaging spectrometer (ISM) is an imaging spectrometer in the range of the near infrared that flew onboard of Soviet probe Phobos 2 in 1989. Its first objective was to obtain information about the mineralogic composition of the soil of Mars and its satellite Phobos, and about the spatial and temporal variability of the Martian atmosphere. In the spectral range of the instrument 0.76-3.16 microns, the radiation emerging from Mars' atmosphere is almost entirely due to the solar radiation reflected by the soil. Therefore, independent knowledge of the spectral transmittance of the atmosphere allows us to eliminate the atmospheric effect from the ISM data and so to obtain the spectral signature of the planet soil. In the present work the Martian atmospheric transmittance has been computed using FASCODE and the spectral lines atlas HITRAN of AFGL. The atmospheric profile has been defined on the basis of the work of Moroz et al. Then, the convolution of the computed transmittance with the response functions of ISM has been carried out to obtain the atmospheric absorption from the measurements it is necessary to renormalize the transmittance computed with FASCODE so that the depth of the absorption bands is the same as that of the bands measured by ISM. Finally, dividing the measured spectra by the computed ones we obtain the spectra signature of Martian soil from which it is possible to deduce the mineralogical composition of the observed zones.

  3. A wavelet analysis for the X-ray absorption spectra of molecules.

    PubMed

    Penfold, T J; Tavernelli, I; Milne, C J; Reinhard, M; El Nahhas, A; Abela, R; Rothlisberger, U; Chergui, M

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO)(3)(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  4. A wavelet analysis for the X-ray absorption spectra of molecules

    SciTech Connect

    Penfold, T. J.; Tavernelli, I.; Rothlisberger, U.; Milne, C. J.; Abela, R.; Reinhard, M.; Nahhas, A. El; Chergui, M.

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  5. Solvent effects on the absorption and fluorescence spectra of rhaponticin: Experimental and theoretical studies

    NASA Astrophysics Data System (ADS)

    Sun, Yang; Liang, Xuhua; Zhao, Yingyong; Fan, Jun

    2013-02-01

    Rhaponticin (RH) possesses a variety of pharmacological activities including potent antitumor, antitumor-promoting, antithrombotic, antioxidant and vasorelaxant effects. The fundamental photophysics of RH is not well understood. In this work, solvent effect on the photoluminescence behavior of RH was studied by fluorescence and absorption spectra. The bathchromic shift was observed in absorption and fluorescence spectra with the increase of solvents polarity, which implied that transition involved was π → π*. A quantitative estimation of the contribution from different solvatochromic parameters, like normalized transition energy value (ETN), was made using the linear stokes shift (Δν) relationship based on the Lippert-Suppan equation. The ground state and excited state dipole moments were calculated by quantum-mechanical second-order perturbation method as a function of the dielectric constant (ɛ) and refractive index (n). The result was found to be 2.23 and 3.67 D in ground state and excited state respectively. The density functional theory (DFT) was used to obtain the most stable structure, electronic excitation energy, dipole moments and charge distribution. The analysis revealed that the RH exhibited strong photoinduced intramolecular charge transfer (ICT), and the intermolecular hydrogen bonding ability of the solvent was the most important parameter to characterize the photophysics behavior of RH. The hydrogen bonding effect occurred at the localized electron-acceptor oxygen at the glycoside bond. The experimental and theoretical results would help us better understand the photophysical properties of RH.

  6. First principles absorption spectra of Cu{sub n} (n = 2 - 20) clusters.

    SciTech Connect

    Baishya, K.; Idrobo, J. C.; Ogut, S.; Yang, M.; Jackson, K. A.; Jellinek, J.

    2011-06-17

    Optical absorption spectra for the computed ground state structures of copper clusters (Cu{sub n}, n = 2-20) are investigated from first principles using time-dependent density functional theory in the adiabatic local density approximation (TDLDA). The results are compared with available experimental data, existing calculations, and with results from our previous computations on silver and gold clusters. The main effects of d electrons on the absorption spectra, quenching the oscillator strengths, and getting directly involved in low-energy excitations increase in going from Ag{sub n} to Au{sub n} to Cu{sub n} due to the increase in the hybridization of the occupied, yet shallow, d orbitals and the partially occupied s orbitals. We predict that while Cu nanoparticles of spherical or moderately ellipsoidal shape do not exhibit Mie (surface plasmon) resonances, unlike the case for Ag and Au, extremely prolate or oblate Cu nanoparticles with eccentricities near unity should give rise to Mie resonances in the lower end of the visible range and in the infrared. This tunable resonance predicted by the classical Mie-Gans theory is reproduced with remarkable accuracy by our TDLDA computations on hypothetical Cu clusters in the form of zigzag chains with as few as 6 to 20 atoms.

  7. Near Edge X-Ray Absorption Fine Structure Spectroscopy with X-Ray Free-Electron Lasers

    SciTech Connect

    Bernstein, D.P.; Acremann, Y.; Scherz, A.; Burkhardt, M.; Stohr, J.; Beye, M.; Schlotter, W.F.; Beeck, T.; Sorgenfrei, F.; Pietzsch, A.; Wurth, W.; Fohlisch, A.; /Hamburg U.

    2009-12-11

    We demonstrate the feasibility of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy on solids by means of femtosecond soft x-ray pulses from a free-electron laser (FEL). Our experiments, carried out at the Free-Electron Laser at Hamburg (FLASH), used a special sample geometry, spectrographic energy dispersion, single shot position-sensitive detection and a data normalization procedure that eliminates the severe fluctuations of the incident intensity in space and photon energy. As an example we recorded the {sup 3}D{sub 1} N{sub 4,5}-edge absorption resonance of La{sup 3+}-ions in LaMnO{sub 3}. Our study opens the door for x-ray absorption measurements on future x-ray FEL facilities.

  8. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  9. Two-photon absorption properties of Dehydrobenzo[12]annulenes and hexakis(phenylethynyl)benzenes: effect of edge-linkage.

    PubMed

    Kamada, Kenji; Antonov, Liudmil; Yamada, Satoru; Ohta, Koji; Yoshimura, Takashi; Tahara, Kazukuni; Inaba, Akiko; Sonoda, Motohiro; Tobe, Yoshito

    2007-12-21

    Two-photon absorption (TPA) properties of two trefoil-shaped compounds with different edge linkages--tris(hexadehydrotribenzo[12]annulene) and tris(tetradehydrotribenzo[12]annulene)--and three asterisk-shaped compounds having no edge-linkage--hexakis(phenylethynyl)benzenes--are investigated experimentally by the open-aperture Z-scan and TPA-induced fluorescence methods with wavelength tuneable femtosecond pulses. The compound with ethynylene edge-linkage exhibits the most intense TPA (the maximal TPA cross section is 1300+/-170 GM at 572 nm where 1 GM=10(-50) cm(4) s molecule(-1) photon(-1)). The TPA activity of the compounds is primarily explained in terms of the planarity of the molecules in relation with the type of edge-linkage.

  10. Nucleic acid vibrational circular dichroism, absorption, and linear dichroism spectra. I. A DeVoe theory approach.

    PubMed Central

    Self, B D; Moore, D S

    1997-01-01

    Infrared (IR) vibrational circular dichroism (VCD), absorption, and linear dichroism (LD) spectra of four homopolyribonucleotides, poly(rA), poly(rG), poly(rC), and poly(rU), have been calculated, in the 1750-1550 cm-1 spectral region, using the DeVoe polarizability theory. A newly derived algorithm, which approximates the Hilbert transform of imaginaries to reals, was used in the calculations to obtain real parts of oscillator polarizabilities associated with each normal mode. The calculated spectra of the polynucleotides were compared with previously measured solution spectra. The good agreement between calculated and measured polynucleotide spectra indicates, for the first time, that the DeVoe theory is a useful means of calculating the VCD and IR absorption spectra of polynucleotides. For the first time, calculated DeVoe theory VCD and IR absorption spectra of oriented polynucleotides are presented. The calculated VCD spectra for the oriented polynucleotides are used to predict the spectra for such measurements made in the future. The calculated IR spectra for the oriented polynucleotides are useful in interpreting the linear dichroism of the polynucleotides. PMID:9199798

  11. Excitation dynamics in Phycoerythrin 545: modeling of steady-state spectra and transient absorption with modified Redfield theory.

    PubMed

    Novoderezhkin, Vladimir I; Doust, Alexander B; Curutchet, Carles; Scholes, Gregory D; van Grondelle, Rienk

    2010-07-21

    We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex.

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

    SciTech Connect

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

    1986-04-01

    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 approx.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.

  13. [Laser induced breakdown spectra of coal sample and self-absorption of the spectral line].

    PubMed

    Zhang, Gui-yin; Ji, Hui; Jin, Yi-dong

    2014-12-01

    The LIBS of one kind of household fuel coal was obtained with the first harmonic output 532 nm of an Nd·YAG laser as radiation source. With the assignment of the spectral lines, it was found that besides the elements C, Si, Mg, Fe, Al, Ca, Ti, Na and K, which are reported to be contained in coal, the presented sample also contains trace elements, such as Cd, Co, Hf, Ir, Li, Mn, Ni, Rb, Sr, V, W, Zn, Zr etc, but the spectral lines corresponding to O and H elements did not appear in the spectra. This is owing to the facts that the transition probability of H and O atoms is small and the energy of the upper level for transition is higher. The results of measurement also show that the intensity of spectral line increases with the laser pulse energy and self-absorption of the spectral lines K766.493 nm and K769.921 nm will appear to some extent. Increasing laser energy further will make self-absorption more obvious. The presence of self-absorption can be attributed to two factors. One is the higher transition rate of K atoms, and the other is that the increase in laser intensity induces the enhancement of the particle number density in the plasma.

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

    PubMed

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

    2016-04-05

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

  15. Dynamics of carbohydrate residues of alpha 1-acid glycoprotein (orosomucoid) followed by red-edge excitation spectra and emission anisotropy studies of Calcofluor White.

    PubMed

    Albani, J R; Sillen, A; Coddeville, B; Plancke, Y D; Engelborghs, Y

    1999-11-23

    Dynamics studies on Calcofluor White bound to the carbohydrate residues of sialylated and asialylated alpha 1-acid glycoprotein (orosomucoid) have been performed. The interaction between the fluorophore and the protein was found to occur preferentially with the glycan residues with a dependence on their spatial conformation. In the presence of sialylated alpha 1-acid glycoprotein, excitation at the red edge of the absorption spectrum of calcofluor does not lead to a shift in the fluorescence emission maximum (440 nm) of the fluorophore. Thus, the emission of calcofluor occurs from a relaxed state. This is confirmed by anisotropy studies as a function of temperature (Perrin plot). In the presence of asialylated alpha 1-acid glycoprotein, red-edge excitation spectra show an important shift (8 nm) of the fluorescence emission maximum of the probe. This reveals that emission of calcofluor occurs before relaxation of the surrounding carbohydrate residues occurs. Emission from a non-relaxed state means that Calcofluor molecules are bound tightly to the carbohydrate residues, a result confirmed by anisotropy studies.

  16. Laboratory studies at high resolution of the infrared absorption spectra of a number of gases found in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Hunt, R. H.

    1983-01-01

    The infrared absorption spectra of a number of gases found in planetary atmospheres were studied at high resolution. Absorption line measurements which can be of value for the interpretation of planetary spectra in terms of molecular abundances and conditions in the planetary atmospheres were provided. The high resolution spectra have yielded measurements of individual vibration rotation line parameters including positions, strengths, pressure broadened widths and, where assignments were unknown, the temperature sensitivity of the strengths. Such information allows the determinations of the absorption of a given molecular gas under planetary conditions of temperature and pressure and at the same time it provides the data necessary if the spectra are to be understood in terms of basic molecular theory. Thus this work has included spectral analysis in the form of line assignments as well as fitting of the data to Hamiltonian models. Such fitting is very useful in that it helps to confirm and extend the assignments.

  17. Absorption-mode Fourier transform mass spectrometry: the effects of apodization and phasing on modified protein spectra.

    PubMed

    Qi, Yulin; Li, Huilin; Wills, Rebecca H; Perez-Hurtado, Pilar; Yu, Xiang; Kilgour, David P A; Barrow, Mark P; Lin, Cheng; O'Connor, Peter B

    2013-06-01

    The method of phasing broadband Fourier transform ion cyclotron resonance (FT-ICR) spectra allows plotting the spectra in the absorption-mode; this new approach significantly improves the quality of the data at no extra cost. Herein, an internal calibration method for calculating the phase function has been developed and successfully applied to the top-down spectra of modified proteins, where the peak intensities vary by 100×. The result shows that the use of absorption-mode spectra allows more peaks to be discerned within the recorded data, and this can reveal much greater information about the protein and modifications under investigation. In addition, noise and harmonic peaks can be assigned immediately in the absorption-mode.

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

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  1. Interaction of vanadium and sulfate in blood cells from the tunicate Ascidia ceratodes: Observations using x-ray absorption edge structure and EPR spectroscopies

    SciTech Connect

    Frank, P.; Hedman, B.; Hodgson, K.O.; Carlson, R.M.K.

    1994-08-17

    Sulfur K-edge X-ray absorption spectroscopy (S-K XAS) and EPR spectroscopy have been used to investigate the inorganic solution chemistry of vanadium, sulfate, and methanesulfonate, with application to blood cells from the tunicate Ascidia ceratodes. Three independent whole blood cell preparations (S85, S86, W87) collected over a period of 18 months were examined. Average blood cell vanadium concentrations were determined to be 0.099, 0.079, and 0.062 M, respectively. All three collections gave sulfur XAS spectra consistent with significant intracellular concentrations of low-valent sulfur, an alkanesulfonic acid, and sulfate. In model studies, the line width of the sulfate K-edge XAS spectrum was found to titrate with both pH and [V(III)]. Application of this finding to A. ceratodes blood cell sulfur XAS spectra provided evidence for direct interactions between endogenous dissolved sulfate and V(III) in two of the three collections. All three collections yielded sulfate XAS edge spectra consistent with low pH. Curve-fitting analysis of the S-K edge XAS spectra for the three whole blood cell collections yielded the ratios of intracellular sulfate:alkane sulfonate:low-valent sulfur to be as follows: S85, 1.0:0.9:0.36;S86, 1.0;0.5;1.5;W87,1.0;0.44:0.24. Comparisons with models indicated that the low-valent blood cell sulfur included various disulfide-like compounds unlike cystine. This all implies a surprisingly rich and variable sulfur biochemistry in these marine organisms. EPR spectroscopy of whole blood cells from one animal from the W87 collection revealed an endogenous VO{sup 2+}-sulfate interaction. Thus both V(III) and VO{sup 2+} can sense an intracellular pool of sulfate, implying the biological colocation of these two metal ions. The variations in blood chemistry observed over time as described herein caution against definitive application of single point experiments.

  2. Influence of substituents on the N K X-ray absorption near-edge structure of pyrrole derivatives

    NASA Astrophysics Data System (ADS)

    Hennig, C.; Hallmeier, K. H.; Bach, A.; Bender, S.; Franke, R.; Hormes, J.; Szargan, R.

    1996-08-01

    The X-ray absorption and electron yield spectra of monomeric pyrrole including derivatives with different substituents, thiazole and oxazole have been investigated. Inductive and mesomeric effects on the spectral features are discussed. Inductive effects create energy shifts of the π ∗ resonances: mesomeric effects cause a splitting and energy shifts of the π ∗ resonances.

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

    PubMed

    Leto, Domenick F; Jackson, Timothy A

    2014-06-16

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

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

    PubMed Central

    2015-01-01

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

  5. Absorption edge subtraction imaging for volumetric measurement in an animal model of malignant brain tumor

    NASA Astrophysics Data System (ADS)

    Rigley, S.; Rigon, L.; Ataelmannan, K.; Chapman, D.; Doucette, R.; Griebel, R.; Juurlink, B.; Arfelli, F.; Menk, R.-H.; Tromba, G.; Barroso, R. C.; Beveridge, T.; Lewis, R.; Pavlov, K.; Siu, K.; Hall, C.; Schültke, E.

    2005-08-01

    The goal of this project is to determine the feasibility of utilizing colloidal gold as a marker for C6 glioblastoma cells implanted into rat brain as an appropriate model for volumetric measurements of tumors using absorption edge subtraction (AES). Phase sensitive X-ray imaging is combined with KES to give good soft tissue contrast. Current methods for volumetric measurements of implanted C6 glioblastoma tumors in rat brains using MRI technology are inadequate due to the small size of the tumor (2.5-4 mm in diameter) and the thickness of the MRI slice (1-1.5 mm). Previously, our group has shown that AES detection of colloidal gold labeled C6 glioblastoma cells implanted into a rat brains may be feasible. The long-term goal for this project is to establish a method, which would allow the researcher to monitor the development of a tumor over time. Most importantly, this technique should allow researchers to accurately determine the potency of a treatment on the size and growth rate for a C6 implanted tumors. In addition, we plan to challenge the hypothesis that tumors of the glioma type do not metastasize outside of the brain. A sensitive technique for the detection of C6 cells, such as that using colloidal gold and AES/DEI, should enable researchers to detect C6 cells, which have metastasized and migrated to different areas of the body. The ability to detect implanted C6 cells followed by the development of the tumor, the possible migration of the cells and the ability to accurately measure the effects of treatments on the volume of the tumor would be of the utmost importance to brain tumor research.

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

    PubMed

    Asmuruf, Frans A; Besley, Nicholas A

    2008-08-14

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

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Error reduction in retrievals of atmospheric species from symmetrically measured lidar sounding absorption spectra.

    PubMed

    Chen, Jeffrey R; Numata, Kenji; Wu, Stewart T

    2014-10-20

    We report new methods for retrieving atmospheric constituents from symmetrically-measured lidar-sounding absorption spectra. The forward model accounts for laser line-center frequency noise and broadened line-shape, and is essentially linearized by linking estimated optical-depths to the mixing ratios. Errors from the spectral distortion and laser frequency drift are substantially reduced by averaging optical-depths at each pair of symmetric wavelength channels. Retrieval errors from measurement noise and model bias are analyzed parametrically and numerically for multiple atmospheric layers, to provide deeper insight. Errors from surface height and reflectance variations are reduced to tolerable levels by "averaging before log" with pulse-by-pulse ranging knowledge incorporated.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Breaking of symmetrical charge distribution in xanthylocyanine chromophores detecting by their absorption spectra

    NASA Astrophysics Data System (ADS)

    Vasyluk, S. V.; Viniychuk, O. O.; Poronik, Ye. M.; Kovtun, Yu. P.; Shandura, M. P.; Yashchuk, V. M.; Kachkovsky, O. D.

    2011-03-01

    A detailed experimental investigation and quantum-chemical analysis of symmetrical cyanines with xanthylium and its substituted derivatives and with different polymethine chain (containing 1 and 2 vinylene groups) have been performed with the goal of understanding the nature of the electronic transitions in molecules. It is established electronic transitions in carbocyanines are similar to that in the typical Brooker's cyanines. In contrast, the absorption spectra of dicarbocyanines demonstrate a strong solvent dependence and substantial band broadening represented by the growth of the short wavelength shoulder. Basing on the results of the quantum-chemical calculation and conception of the mobile solitonic-like charge waves, we have concluded that the dicarbocyanines exist in two charged forms in the ground state with symmetrical and unsymmetrical distributions of the charge density. These are the examples of the cationic cyanines with the shortest chain when the symmetry breaking occurs.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    DOE PAGES

    Alkire, Randall W.

    2016-11-01

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

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

    SciTech Connect

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

    2013-03-10

    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{sub 2}O and O{sub 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{sub 2}O and O{sub 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{sub 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.

  14. Atomic form factors and photoelectric absorption cross-sections near absorption edges in the soft X-ray region

    SciTech Connect

    Chantler, C.

    2006-11-09

    Reliable knowledge of the complex X-ray form factor [Re(f) and Im(f)] and the photoelectric attenuation coefficient ({delta}{sub PE}) is required for crystallography, medical diagnosis, radiation safety and XAFS studies. Key discrepancies in earlier theoretical work are due to the smoothing of edge structure, the use of non-relativistic wave functions, and the lack of appropriate convergence of wave functions. These discrepancies lead to significant corrections for most comprehensive (i.e. all-Z) tabulations. This work has led to a major comprehensive database tabulation [Chantler, C. T. (2000). J. Phys. Chem. Ref. Data, 29, 597-1048] which serves as a sequel and companion to earlier relativistic Dirac-Fock computations [Chantler, C. T. (1995). J. Phys. Chem. Ref. Data, 24, 71-643]. The paper finds that earlier work needs improvement in the near-edge region for soft X-ray energies, and derives new theoretical results of substantially higher accuracy in near-edge soft X-ray regions. Fine grids near edges are tabulated demonstrating the current comparison with alternate theory and with available experimental data. The best experimental data and the observed experimental structure as a function of energy are strong indicators of the validity of the current approach. New developments in experimental measurement hold great promise in making critical comparisons with theory in the near future.

  15. Atomic form factors and photoelectric absorption cross-sections near absorption edges in the soft X-ray region

    SciTech Connect

    Chantler, C.T.

    2003-01-24

    Reliable knowledge of the complex X-ray form factor [Re(f) and Im(f)] and the photoelectric attenuation coefficient ({sigma}PE) is required for crystallography, medical diagnosis, radiation safety and XAFS studies. Key discrepancies in earlier theoretical work are due to the smoothing of edge structure, the use of non-relativistic wave functions, and the lack of appropriate convergence of wave functions. These discrepancies lead to significant corrections for most comprehensive (i.e. all-Z) tabulations. This work has led to a major comprehensive database tabulation [Chantler, C. T. (2000). J. Phys. Chem. Ref. Data, 29, 597-1048] which serves as a sequel and companion to earlier relativistic Dirac-Fock computations [Chantler, C. T. (1995). J. Phys. Chem. Ref. Data, 24, 71-643]. The paper finds that earlier work needs improvement in the near-edge region for soft X-ray energies, and derives new theoretical results of substantially higher accuracy in near-edge soft X-ray regions. Fine grids near edges are tabulated demonstrating the current comparison with alternate theory and with available experimental data. The best experimental data and the observed experimental structure as a function of energy are strong indicators of the validity of the current approach. New developments in experimental measurement hold great promise in making critical comparisons with theory in the near future. This work forms the latest component of the FFAST NIST database [http://physics.nist.gov/PhysRefData/FFast02/Text/cover.html].

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Extended X- ray absorption fine structure study at the K-edge of copper in mixed ligand complexes having benzimidazole as one of the ligands

    NASA Astrophysics Data System (ADS)

    Hinge, V. K.; Joshi, S. K.; Nitin Nair, N.; Singh Verma, Vikram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

    2014-09-01

    Extended X-ray absorption fine structure (EXAFS) spectra have been studied at the K-edge of copper in some of its biologically important complexes, viz., [Cu(BzImH)4X2] and [Cu(BzIm)2], where X= Cl, Br, 1/2SO4, ClO4, NO3, and BzIm = Benzimidazolato anion. The spectra have been recorded using a bent crystal 0.4 m Cauchois-type transmission spectrograph. The positions of EXAFS maxima and minima have been used to determine the bond lengths in the complexes with the help of three different methods, namely, Levy's, Lytle's and Lytle, Sayers and Stern's (L.S.S.) methods. The phase uncorrected bond lengths have also been determined from Fourier transforms of the experimental spectra. The results obtained from these methods have been discussed and it has been found that the results obtained by L.S.S. method are comparable with the results obtained by Fourier transformation method and that these two methods give phase uncorrected bond lengths.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Porta, A.; Zakari-Issoufou, A.-A.; Fallot, M.; Algora, A.; Tain, J. L.; Valencia, E.; Rice, S.; Bui, V. M.; Cormon, S.; Estienne, M.; Agramunt, J.; Äystö, J.; Bowry, M.; Briz, J. A.; Caballero-Folch, R.; Cano-Ott, D.; Cucouanes, A.; Elomaa, V.-V.; Eronen, T.; Estévez, E.; Farrelly, G. F.; Garcia, A. R.; Gelletly, W.; Gomez-Hornillos, M. B.; Gorlychev, V.; Hakala, J.; Jokinen, A.; Jordan, M. D.; Kankainen, A.; Karvonen, P.; Kolhinen, V. S.; Kondev, F. G.; Martinez, T.; Mendoza, E.; Molina, F.; Moore, I.; Perez-Cerdán, A. B.; Podolyák, Zs.; Penttilä, H.; Regan, P. H.; Reponen, M.; Rissanen, J.; Rubio, B.; Shiba, T.; Sonzogni, A. A.; Weber, C.

    2016-03-01

    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.

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

    PubMed

    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.

  2. Polarized absorption spectra of single crystals of lunar pyroxenes and olivines.

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Huggins, F. E.; Abu-Eid, R. M.

    1972-01-01

    Measurements have been made of the polarized absorption spectra (360-2200 nm) of compositionally zoned pyroxene minerals in rocks 10045, 10047 and 10058 and olivines in rocks 10020 and 10022. The Apollo 11 pyroxenes with relatively high Ti/Fe ratios were chosen initially to investigate the presence of crystal field spectra of Fe(2+) and Ti(3+) ions in the minerals. Broad intense bands at about 1000 and 2100 nm arise from spin-allowed, polarization-dependent transitions in Fe(2+) ions in pyroxenes. Several weak sharp peaks occur in the visible region. Peaks at 402, 425, 505, 550, and 585 nm represent spin-forbidden transitions in Fe(2+) ions, while broader bands at 460-470 nm and 650-660 nm are attributed to Ti(3+) ions. Charge transfer bands, which in terrestrial pyroxenes often extend into the visible region, are displaced to shorter wavelengths in lunar pyroxenes. This feature correlates with the absence of Ti(3+) ions in these minerals.

  3. C-13 NMR chemical shifts and visible absorption spectra of unsymmetrical fluoran dye by MO calculations

    NASA Astrophysics Data System (ADS)

    Hoshiba, T.; Ida, T.; Mizuno, M.; Otsuka, T.; Takaoka, K.; Endo, K.

    2002-01-01

    An unsymmetrical fluoran dye, 3-diethylamino-6-methyl-7-chlorofluoran (DEAMCF) is one of the leuco dyes which shows the coloring-to-decoloring reversible reaction with acidity. We calculated the 13C chemical shieldings of the DEAMCF with the frame model compounds using ab initio gauge invariant atomic orbital methods, and compared it with the experimental shifts. The calculated values of the frame compounds are in good agreement with the experimental ones in the error range of -4.9-16.7 ppm. The calculated ones for the decolored-form of the DEAMCF reflected the observed ones, although the errors range from -13.4 to 23.1 ppm. Furthermore, we analyzed the UV-Visible absorption spectra of the decolored and colored forms of DEAMCF by a semiempirical ZINDO MO method. For the colored form, the observed absorption peaks at 550 and 510 nm correspond to the excitation from π-bonding HOMO (π-electrons which conjugated in xanthene ring) and π-bonding nearest HOMO (π-electrons concentrated in benzene-ring with methyl and Cl groups of xanthene) to π ∗-antibonding LUMO (π ∗-electrons of xanthene), respectively.

  4. Ultraviolet spectra of quenched carbonaceous composite derivatives: Comparison to the '217 nanometer' interstellar absorption feature

    NASA Technical Reports Server (NTRS)

    Sakata, Akira; Wada, Setsuko; Tokunaga, Alan T.; Narisawa, Takatoshi; Nakagawa, Hidehiro; Ono, Hiroshi

    1994-01-01

    QCCs (quenched carbonaceous composite) are amorphus carbonaceous material formed from a hydrocarbon plasma. We present the UV-visible spectra of 'filmy QCC; (obtained outside of the beam ejected from the hydrocarbon plasma) and 'dark QCC' (obtained very near to the beam) for comparison to the stellar extinction curve. When filmy QCC is heated to 500-700 C (thermally altered), the wavelength of the absorption maximum increases form 204 nm to 220-222 nm. The dark QCC has an absorption maximum at 217-222 nm. In addition, the thermally altered filmy QCC has a slope change at about 500 nm which resmbles that in the interstellar extinction curve. The resemblance of the extinction curve of the QCCs to that of the interstellar medium suggests that QCC derivatives may be representative of the type of interstellar material that produces the 217 nm interstellar medium feature. The peak extinction of the dark QCC is higher than the average interstellar extinction curve while that of the thermally altered filmy QCC is lower, so that a mixture of dark and thermally altered filmy QCC can match the peak extinction observed in the interstellar medium. It is shown from electron micrographs that most of the thermally altered flimy QCC is in the form of small grainy structure less than 4 nm in diameter. This shows that the structure unit causing the 217-222 nm feature in QCC is very small.

  5. A combination spectrophotometer for measuring electronic absorption, natural circular dichroism, and magnetic circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Policke, Timothy A.; Schreiner, Anton F.; Trexler, Jack W.; Knopp, James A.

    1990-08-01

    The design, construction, and evaluation of a combination spectrometer for measuring electronic absorption (EA), natural circular dichroism (CD), and magnetic circular dichroism (MCD) are described. Around the optical components of a JASCO ORD/UV-5 spectropolarimeter, a new EA/CD/MCD instrument was built with the realized intentions of increasing sensitivity and upgrading the analog tube type circuitry to a solid-state digitally, computer-controlled spectrophotometer. It is a flexible, dynamic, and user-controllable system, interfaced to an Apple II Plus computer, for studying instrument and signal parameters. The monochromator (M), photoelastic modulator (PEM), photomultiplier tube applied voltage (PMHV), and photomultiplier tube dc output current (PMdc) are under complete and independent software control. Our system has two unique aspects for obtaining the circular dichroism. First, the ac signal is measured with a voltage-to-frequency (V/f) converter; and, second, both the ac and the dc are independently recorded and their ratio is digitally calculated. This design has several advantages which include the elimination of voltage divider integrated circuits or division electronics, a wide dynamic range, a greater precision of ac values at low percentages of full scale, and the capability of continuous integration over long time periods. Also, both types of spectra, EA and CD or MCD, are obtained from the current output of the PM. This paper not only describes the design of the instrument for obtaining the two types of spectra but also compares four methods of obtaining the circular dichroism. Sensitivities of ˜1×10-7ΔA units are achievable as determined by measuring CD spectra of the well-known enantiomer (+)-[Co(en)3]3+.

  6. XANES (X-ray Absorption Near Edge Structure) investigation of cerium as an inhibitor for Al alloys

    SciTech Connect

    Davenport, A.J.; Isaacs, H.S. ); Kendig, M.W. . Science Center)

    1991-01-01

    Cerium ions are under investigation as possible replacements for toxic chromates. The use of cerium ions as corrosion inhibitors for aluminum alloys is investigated using XANES (x-ray absorption near edge structure). On immersion in a dilute solution of cerium ions, cerium is incorporated into the oxide films on aluminum alloys in either the 3- or 4-valent state depending upon the alloy and on the surface preparation. 7 refs., 2 figs.

  7. Absorption spectra of isomeric OH adducts of 1,3,7-trimethylxanthine

    SciTech Connect

    Vinchurkar, M.S.; Rao, B.S.M.; Mohan, H.; Mittal, J.P.; Schmidt, K.H.; Jonah, C.D.

    1997-04-17

    The reactions of OH{sup .}, O{sup .-}, and SO{sub 4}{sup .-} with 1,3,7-trimethylxanthine (caffeine) were studied by pulse radiolysis with optical and conductance detection techniques. The absorption spectra of transients formed in OH{sup .} reaction in neutral solutions exhibited peaks at 310 and 335 nm, as well as a broad absorption maximum at 500 nm, which decayed by first-order kinetics. The rate (k = (4.0 {+-} 0.5) x 10{sup 4} s{sup -1}) of this decay is independent of pH in the range 4-9 and is in agreement with that determined from the conductance detection (k = 4 x 10{sup 4} s{sup -1}). The spectrum in acidic solutions has only a broad peak around 330 nm with no absorption in the higher wavelength region. The intermediates formed in reaction of O{sup .-} absorb around 310 and at 350 nm, and the first-order decay at the latter wavelength was not seen. The OH radical adds to C-4 (X-40H{sup .}) and C-8 (X-80H{sup .}) positions of caffeine in the ratio 1:2 as determined from the redox titration and conductivity measurements. H abstraction from the methyl group is an additional reaction channel in O{sup .-} reaction. Dehydroxylation of the X-40H{sup .} adduct occurs, whereas the X-80H{sup .} adduct does not undergo ring opening. The spectrum obtained for OH{sup .} reaction in oxygenated solutions is similar to that observed in SO{sub 4}{sup .-} reaction in basic solutions. 25 refs., 5 figs., 1 tab.

  8. A mixed quantum-classical description of pheophorbide a linear absorption spectra: Quantum-corrections of the Qy- and Qx-absorption vibrational satellites

    NASA Astrophysics Data System (ADS)

    Megow, Jörg; Kulesza, Alexander; May, Volkhard

    2016-01-01

    The ground-state classical path approximation is utilized to compute molecular absorption spectra in a mixed quantum-classical frame. To improve the description for high-frequency vibrational satellites, related quantum correction factors are introduced. The improved method is demonstrated for the Qy- and Qx-bands of pheophorbide a.

  9. Soft X-ray absorption spectra in the 0 K region of microporous carbon and some reference aromatic compounds

    SciTech Connect

    Muramatsu, Yasuji; Kuramoto, Kentaro; Gullikson, Eric M.; Perera, Rupert C.C.

    2003-06-01

    To analyze the oxidation states of the graphitic surface of microporous carbon, soft X-ray absorption spectra in the 0 K region have been obtained for microporous carbon and various aromatic compounds. The aromatic molecules studied are substituted with one or more of the following oxygenated functional groups: hydroxy (-OH), carboxy (-COOH), carbonyl (>C=O), formyl (-CH=O), and ether (-O-). From comparison of the soft X-ray absorption spectra of microporous carbon and of reference aromatic compounds, the most probable chemical bonding states of oxygen in microporous carbon are found to be -COOH and >C(H)=O. Spectral features in the soft X-ray absorption spectra of microporous carbon are well explained by the O2p density of states in these oxygenated functional groups from discrete variational (DV)-X{alpha} molecular orbital calculations.

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

    SciTech Connect

    Perez-Caro, M.; Rodriguez, A. G.; Vidal, M. A.; Navarro-Contreras, H.

    2010-07-15

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

  11. The dust-scattering component of X-ray extinction: effects on continuum fitting and high-resolution absorption edge structure

    NASA Astrophysics Data System (ADS)

    Corrales, L. R.; García, J.; Wilms, J.; Baganoff, F.

    2016-05-01

    Small angle scattering by dust grains causes a significant contribution to the total interstellar extinction for any X-ray instrument with sub-arcminute resolution (Chandra, Swift, XMM-Newton). However, the dust-scattering component is not included in the current absorption models: phabs, TBabs, and TBnew. We simulate a large number of Chandra spectra to explore the bias in the spectral fit and NH measurements obtained without including extinction from dust scattering. We find that without incorporating dust scattering, the measured NH will be too large by a baseline level of 25 per cent. This effect is modulated by the imaging resolution of the telescope, because some amount of unresolved scattered light will be captured within the aperture used to extract point source information. In high-resolution spectroscopy, dust scattering significantly enhances the total extinction optical depth and the shape of the photoelectric absorption edges. We focus in particular on the Fe-L edge at 0.7 keV, showing that the total extinction template fits well to the high-resolution spectrum of three X-ray binaries from the Chandra archive: GX 9+9, XTE J1817-330, and Cyg X-1. In cases where dust is intrinsic to the source, a covering factor based on the angular extent of the dusty material must be applied to the extinction curve, regardless of angular imaging resolution. This approach will be particularly relevant for dust in quasar absorption line systems and might constrain clump sizes in active galactic nuclei.

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

    PubMed

    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.

  13. [Characteristics of the absorption spectra of the mixtures of C42(Al), C32 (Si) and so on].

    PubMed

    Chen, W

    1998-12-01

    The mixtures containing C42 (A1), C32 (Si), C30 (Ca) and C28 (Fe) are produced by means of arc discharge and He gas convection. The spectra are measured and compared with the absorption spectra of all carbon molecules. The result shows that after imbeded in all carbon molecules, the Al, Si, Ca and Fe atoms do not change the positions of the absorption peak of original molecules, but only change the probability of pi --> pi* transition and n --> pi* transition of these molecules.

  14. Solvent effects on the steady-state absorption and fluorescence spectra of uracil, thymine and 5-fluorouracil.

    PubMed

    Gustavsson, Thomas; Sarkar, Nilmoni; Bányász, Akos; Markovitsi, Dimitra; Improta, Roberto

    2007-01-01

    We report a comparison of the steady-state absorption and fluorescence spectra of three representative uracil derivatives (uracil, thymine and 5-fluorouracil) in alcoholic solutions. The present results are compared with those from our previous experimental and computational studies of the same compounds in water and acetonitrile. The effects of solvent polarity and hydrogen bonding on the spectra are discussed in the light of theoretical predictions. This comparative analysis provides a more complete picture of the solvent effects on the absorption and fluorescence properties of pyrimidine nucleobases, with special emphasis on the mechanism of the excited state deactivation.

  15. Optical Absorption Spectra and Excitons of Dye-Substrate Interfaces: Catechol on TiO2(110).

    PubMed

    Mowbray, Duncan John; Migani, Annapaola

    2016-06-14

    Optimizing the photovoltaic efficiency of dye-sensitized solar cells (DSSC) based on staggered gap heterojunctions requires a detailed understanding of sub-band gap transitions in the visible from the dye directly to the substrate's conduction band (CB) (type-II DSSCs). Here, we calculate the optical absorption spectra and spatial distribution of bright excitons in the visible region for a prototypical DSSC, catechol on rutile TiO2(110), as a function of coverage and deprotonation of the OH anchoring groups. This is accomplished by solving the Bethe-Salpeter equation (BSE) based on hybrid range-separated exchange and correlation functional (HSE06) density functional theory (DFT) calculations. Such a treatment is necessary to accurately describe the interfacial level alignment and the weakly bound charge transfer transitions that are the dominant absorption mechanism in type-II DSSCs. Our HSE06 BSE spectra agree semiquantitatively with spectra measured for catechol on anatase TiO2 nanoparticles. Our results suggest deprotonation of catechol's OH anchoring groups, while being nearly isoenergetic at high coverages, shifts the onset of the absorption spectra to lower energies, with a concomitant increase in photovoltaic efficiency. Further, the most relevant bright excitons in the visible region are rather intense charge transfer transitions with the electron and hole spatially separated in both the [110] and [001] directions. Such detailed information on the absorption spectra and excitons is only accessible via periodic models of the combined dye-substrate interface.

  16. Anomalous Series of Bands in the Edge Emission Spectra of CdS(О)

    NASA Astrophysics Data System (ADS)

    Morozova, N. K.; Kanakhin, A. A.; Galstyan, V. G.; Shnitnikov, A. S.

    2015-02-01

    The region of the edge emission spectrum of CdS(O) single crystals with cadmium excess is examined. An anomalous series of equidistant bands with leading line at 514 nm and phonon replicas has been revealed. These bands grow in intensity with increase of the excitation density up to 1026-1027 cm-3ṡs-1 at 80 K, and the leading line of the series is observed even at 300 K. It is shown that luminescence is conditioned by the exciton spectrum in perfect bulk single-crystals of CdO. Some characteristics of this spectrum are presented, in particular, the dependence on temperature, excitation intensity, composition and size of the crystals, and the LO interaction. The results experimentally confirm the theoretically calculated magnitude of the direct band gap of CdO.

  17. Refinement of DNA structures through near-edge X-ray absorption fine structure analysis: applications on guanine and cytosine nucleobases, nucleosides, and nucleotides.

    PubMed

    Hua, Weijie; Gao, Bin; Li, Shuhua; Agren, Hans; Luo, Yi

    2010-10-21

    In this work we highlight the potential of NEXAFS—near-edge X-ray absorption fine structure—analysis to perform refinements of hydrogen-bond structure in DNA. For this purpose we have carried out first-principle calculations of the N1s NEXAFS spectra of the guanine and cytosine nucleobases and their tautomers, nucleosides, and nucleotides in the gas phase, as well as for five crystal structures of guanine, cytosine, or guanosine. The spectra all clearly show imine (π1*) and amine (π2*) nitrogen absorption bands with a characteristic energy difference (Δ). Among all of the intramolecule covalent connections, the tautomerism of hydrogens makes the largest influence, around ±0.4−0.5 eV change of Δ, to the spectra due to a switch of single−double bonds. Deoxyribose and ribose sugars can cause at most 0.2 eV narrowing of Δ, while the phosphate groups have nearly negligible effects on the spectra. Two kinds of intermolecule interactions are analyzed, the hydrogen bonds and the stacking effect, by comparing “compressed” and “expanded” models or by comparing models including or excluding the nearest stacking molecules. The shortening of hydrogen-bond length by 0.2−0.3 Å can result in the reduction of Δ by 0.2−0.8 eV. This is because the hydrogen bonds make the electrons more delocalized, and the amine and imine nitrogens become less distinguishable. Moreover, the hydrogen bond has a different ability to influence the spectra of different crystals, with guanine crystals as the largest (change by 0.8 eV) and the guanosine crystal as the smallest (change by 0.2 eV). The stacking has negligible effects on the spectra in all studied systems. A comparison of guanosine to guanine crystals shows that the sugars in the crystal could create “blocks” in the π-and hydrogen bonds network of bases and thus makes the imine and amine nitrogens more distinguishable with a larger Δ. Our theoretical calculations offer a good match with experimental findings

  18. The effect of temperature and pressure on optical absorption spectra of transition zone minerals - Implications for the radiative conductivity of the Earth's interior

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Jacobsen, S. D.; Bina, C. R.; Goncharov, A. F.; Frost, D. J.; McCammon, C. A.

    2010-12-01

    Optical absorption spectra of high-pressure minerals can be used as indirect tools to calculate radiative conductivities of the Earth’s interior [e.g., 1]. Recent high-pressure studies imply that e.g. ringwoodite, γ-(Mg,Fe)2SiO4, does not become opaque in the near infrared and visible region, as previously assumed, but remains transparent to 21.5 GPa [2]. Therefore, it has been concluded that radiative heat transfer does not necessarily become blocked at high pressures of the mantle and ferromagnesian minerals actually might contribute to the heat flow in the Earth’s interior [2]. However, experimental results on temperature effects on radiative heat transfer are not available. We studied the effect of both, pressure and temperature, on the optical absorption of hydrous Fe-bearing ringwoodite, γ-(Mg,Fe)2SiO4, and hydrous Fe-bearing wadsleyite, β-(Mg,Fe)2SiO4, which are the main components of the Earth’s transition zone. Gem-quality single-crystals were synthesized at 18 GPa and 1400 °C in a 5000t multianvil apparatus. Crystals were analyzed by Mössbauer and Raman spectroscopy, electron microprobe analysis and single-crystal X-ray diffraction. For optical absorption measurements in the IR - VIS - UV spectral range (400 - 50000 cm-1) 50 µm sized single-crystals of ringwoodite and wadsleyite were double polished to thicknesses of 13 µm and 18 µm, respectively, and loaded in resistively heated diamond-anvil cells with argon as pressure medium. After taking measurements at high pressure and room temperature, ringwoodite was studied at 26 GPa up to 650 °C and wadsleyite spectra were recorded at 16 GPa up to 450 °C. At ambient pressure the absorption spectrum of ringwoodite reveals a crystal field band (Fe2+) at 12075 cm-1, an intervalence charge transfer band (Fe2+ to Fe3+) at 16491 cm-1, and an absorption edge due to ligand-metal charge transfer close to 30000 cm-1. The wadsleyite spectrum is characterized by a similar absorption edge in the VIS-UV range

  19. Vanadium K-edge X-ray-absorption spectroscopy of the functioning and thionine-oxidized forms of the VFe-protein of the vanadium nitrogenase from Azotobacter chroococcum.

    PubMed Central

    Arber, J M; Dobson, B R; Eady, R R; Hasnain, S S; Garner, C D; Matsushita, T; Nomura, M; Smith, B E

    1989-01-01

    Vanadium K-edge X-ray-absorption spectra were collected for samples of thionine-oxidized, super-reduced (during enzyme turnover) and dithionite-reduced VFe-protein of the vanadium nitrogenase of Azotobacter chroococcum (Acl*). Both the e.x.a.f.s and the x.a.n.e.s. (X-ray-absorption near-edge structure) are consistent with the vanadium being present as part of a VFeS cluster; the environment of the vanadium is not changed significantly in different oxidation states of the protein. The vanadium atom is bound to three oxygen (or nitrogen), three sulphur and three iron atoms at 0.215(3), 0.231(3) and 0.275(3) nm respectively. PMID:2730564

  20. High repetition rate laser produced soft x-ray source for ultrafast x-ray absorption near edge structure measurements.

    PubMed

    Fourmaux, S; Lecherbourg, L; Harmand, M; Servol, M; Kieffer, J C

    2007-11-01

    Recent progress in high intensity ultrafast laser systems provides the opportunity to produce laser plasma x-ray sources exhibiting broad spectrum and high average x-ray flux that are well adapted to x-ray absorption measurements. In this paper, the development of a laser based x-ray absorption near edge structure (XANES) beamline exhibiting high repetition rate by using the Advanced Laser Light Source (ALLS) facility 100 Hz laser system (100 mJ, 35 fs at 800 nm) is presented. This system is based on a broadband tantalum solid target soft x-ray source and a grazing incidence grating spectrometer in the 1-5 nm wavelength range. To demonstrate the high potential of this laser based XANES technique in condensed matter physics, material science, or biology, measurements realized with several samples are presented: VO2 vanadium L edge, Si3N4 nitrogen K edge, and BPDA/PPD polyimide carbon K edge. The characteristics of this laser based beamline are discussed in terms of brightness, signal to noise ratio, and compared to conventional synchrotron broadband x-ray sources which allow achieving similar measurements. Apart from the very compact size and the relative low cost, the main advantages of such a laser based soft x-ray source are the picosecond pulse duration and the perfect synchronization between this x-ray probe and a laser pulse excitation which open the way to the realization of time resolved x-ray absorption measurements with picosecond range time resolution to study the dynamics of ultrafast processes and phase transition.

  1. Temperature dependent electronic structure of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film probed by X-ray absorption near edge structure

    SciTech Connect

    Zhang, Bangmin; Sun, Cheng-Jun E-mail: msecgm@nus.edu.sg; Heald, Steve M.; Chen, Jing-Sheng; Moog Chow, Gan E-mail: msecgm@nus.edu.sg; Venkatesan, T.

    2014-05-07

    The Mn K edge X-ray absorption near edge structures (XANES) of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film (100 nm) on (001) LaAlO{sub 3} substrate was measured at different temperatures to probe the MnO{sub 6} octahedron distortion and corresponding electronic structure. The absorption of high temperature paramagnetic-insulator phase differed from that of the low temperature ferromagnetic-metal phase. The temperature-dependent absorption intensity of Mn K edge XANES was correlated with the relaxation of distorted MnO{sub 6} octahedron, which changed the crystal field acting on the Mn site and the related electronic structure and properties. At low temperature, the splitting of Mn majority e{sub g} orbitals decreased and the density of states above the Fermi level increased in the relaxed MnO{sub 6} octahedron, as reflected by a wider separation between two sub-peaks in the pre-edge XANES spectra.

  2. The manifestation of optical centers in UV-Vis absorption and luminescence spectra of white blood human cells

    NASA Astrophysics Data System (ADS)

    Terent'yeva, Yu G.; Yashchuk, V. M.; Zaika, L. A.; Snitserova, O. M.; Losytsky, M. Yu

    2016-12-01

    A white blood human cells spectral investigation is presented. The aim of this series of experiments was to obtain and analyze the absorption and luminescence (fluorescence and phosphorescence) spectra at room temperature and at 78 K of newly isolated white blood human cells and their organelles. As a result the optical centers and possible biochemical components that form the studied spectra where identified. Also the differences between the spectra of abnormal cells (B-cell chronic lymphocytic leukemia BCLL) and normal ones were studied for the whole cells and individual organelles.

  3. Absorption spectra of garnet films between 1. 0 and 1. 8. mu. m by guided-wave optical spectroscopy

    SciTech Connect

    Olivier, M.; Peuzin, J.; Danel, J.; Challeton, D.

    1981-01-15

    Continuous recording of the absorption spectra of thin films by an optical guided-wave technique is demonstrated. In the case of a garnet thin film of compositoin (YSmLuCa)/sub 3/(FeGe)/sub 5/O/sub 12/ it is shown that the near-infrared Sm/sup 3 +/ absorption bands are clearly visible in contrast with conventional transmission measurement. Comparison with the absorption spectrum of bulk Sm/sub 3/Fe/sub 5/O/sub 12/ garnet allows the determination of an Sm concentration in the film.

  4. Radiative ablation with two ionizing fronts when opacity displays a sharp absorption edge.

    PubMed

    Poujade, Olivier; Bonnefille, Max; Vandenboomgaerde, Marc

    2015-11-01

    The interaction of a strong flux of photons with matter through an ionizing front (I-front) is an ubiquitous phenomenon in the context of astrophysics and inertial confinement fusion (ICF) where intense sources of radiation put matter into motion. When the opacity of the irradiated material varies continuously in the radiation spectral domain, only one single I-front is formed. In contrast, as numerical simulations tend to show, when the opacity of the irradiated material presents a sharp edge in the radiation spectral domain, a second I-front (an edge front) can form. A full description of the mechanism behind the formation of this edge front is presented in this article. It allows us to understand extra shocks (edge-shocks), displayed by ICF simulations, that might affect the robustness of the design of fusion capsules in actual experiments. Moreover, it may have consequences in various domains of astrophysics where ablative flows occur.

  5. Detection of water vapour absorption around 363nm in measured atmospheric absorption spectra and its effect on DOAS evaluations

    NASA Astrophysics Data System (ADS)

    Lampel, Johannes; Polyansky, Oleg. L.; Kyuberis, Alexandra A.; Zobov, Nikolai F.; Tennyson, Jonathan; Lodi, Lorenzo; Pöhler, Denis; Frieß, Udo; Platt, Ulrich; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Water vapour is known to absorb light from the microwave region to the blue part of the visible spectrum at a decreasing magnitude. Ab-initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines until its dissociation limit at 243 nm. We present first evidence of water vapour absorption at 363 nm from field measurements based on the POKAZATEL absorption line list by Polyansky et al. (2016) using data from Multi-Axis differential optical absorption spectroscopy (MAX-DOAS) and Longpath (LP)-DOAS measurements. The predicted absorptions contribute significantly to the observed optical depths with up to 2 × 10-3. Their magnitude correlates well (R2 = 0.89) to simultaneously measured well-established water vapour absorptions in the blue spectral range from 452-499 nm, but is underestimated by a factor of 2.6 ± 0.6 in the ab-initio model. At a spectral resolution of 0.5nm this leads to a maximum absorption cross-section value of 5.4 × 10-27 cm2/molec at 362.3nm. The results are independent of the employed cross-section data to compensate for the overlayed absorption of the oxygen dimer O4. The newly found absorption can have a significant impact on the spectral retrieval of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO are discussed.

  6. Analysis of atmospheric trace constituents from high resolution infrared balloon-borne and ground-based solar absorption spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Rinsland, C. P.; Blatherwick, R. D.; Murcray, F. H.; Murcray, D. G.

    1991-01-01

    Results of ongoing studies of high-resolution solar absorption spectra aimed at the identification and quantification of trace constituents of importance in the chemistry of the stratosphere and upper troposphere are presented. An analysis of balloon-borne and ground-based spectra obtained at 0.0025/cm covering the 700-2200/cm interval is presented. The 0.0025/cm spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of quantifying trace constituents. Results for COF2, F22, SF6, and other species are presented. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra are also discussed.

  7. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice.

    PubMed

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-11-20

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures.

  8. Quantum simulation of thermally-driven phase transition and oxygen K-edge x-ray absorption of high-pressure ice

    PubMed Central

    Kang, Dongdong; Dai, Jiayu; Sun, Huayang; Hou, Yong; Yuan, Jianmin

    2013-01-01

    The structure and phase transition of high-pressure ice are of long-standing interest and challenge, and there is still a huge gap between theoretical and experimental understanding. The quantum nature of protons such as delocalization, quantum tunneling and zero-point motion is crucial to the comprehension of the properties of high-pressure ice. Here we investigated the temperature-induced phase transition and oxygen K-edge x-ray absorption spectra of ice VII, VIII and X using ab initio path-integral molecular dynamics simulations. The tremendous difference between experiments and the previous theoretical predictions is closed for the phase diagram of ice below 300 K at pressures up to 110 GPa. Proton tunneling assists the proton-ordered ice VIII to transform into proton-disordered ice VII where only thermal activated proton-transfer cannot occur. The oxygen K edge with its shift is sensitive to the order-disorder transition, and therefore can be applied to diagnose the dynamics of ice structures. PMID:24253589

  9. Energy-Specific Equation-of-Motion Coupled-Cluster Methods for High-Energy Excited States: Application to K-edge X-ray Absorption Spectroscopy.

    PubMed

    Peng, Bo; Lestrange, Patrick J; Goings, Joshua J; Caricato, Marco; Li, Xiaosong

    2015-09-08

    Single-reference techniques based on coupled-cluster (CC) theory, in the forms of linear response (LR) or equation of motion (EOM), are highly accurate and widely used approaches for modeling valence absorption spectra. Unfortunately, these equations with singles and doubles (LR-CCSD and EOM-CCSD) scale as O(N⁶), which may be prohibitively expensive for the study of high-energy excited states using a conventional eigensolver. In this paper, we present an energy-specific non-Hermitian eigensolver that is able to obtain high-energy excited states (e.g., XAS K-edge spectrum) at low computational cost. In addition, we also introduce an improved trial vector for iteratively solving the EOM-CCSD equation with a focus on high-energy eigenstates. The energy-specific EOM-CCSD approach and its low-scaling alternatives are applied to calculations of carbon, nitrogen, oxygen, and sulfur K-edge excitations. The results are compared to other implementations of CCSD for excited states, energy-specific linear response time-dependent density functional theory (TDDFT), and experimental results with multiple statistical metrics are presented and evaluated.

  10. High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

    NASA Technical Reports Server (NTRS)

    Sonneborn, G.; Iping, R. C.; Gull, T. R.; Vieira, G.

    2003-01-01

    Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127- 22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg 11, Fe II, V II, etc observed in STIS/E230H spectra. The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-l above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30 x 30 arcsec for FUSE, 0.2 x 0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic minimum in 2003.

  11. Transient absorption and luminescence spectra of K9 glass at sub-damage site by ultraviolet laser irradiation

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Huang, J.; Geng, F.; Zhou, X. Y.; Feng, S. Q.; Cheng, X. L.; Jiang, X. D.; Wu, W. D.; Zheng, W. G.; Tang, Y. J.

    2014-01-01

    Transient absorption and luminescence spectra at sub-damage site of K9 glass by laser irradiation at 355 nm are presented. The dependence of transient absorption on laser energy and number of pulses was investigated. As the energy density increases to 2.54 and 3.18 J/cm2, the transient absorption intensity reaches to about 0.20 range from 400 to 480 nm. With the increase of number of pulses the process of residual absorption appears, which can be used to explain the fatigue effect of K9 glass. The defects in K9 glass were investigated by fluorescence and Raman spectra. The fluorescence band centered at about 410 nm is attributed to oxygen deficiency centers. The mechanism of two-photon ionization plays a critical role at sub-damage site. Compared to the Raman spectra of pristine site, intensity of Raman spectra is very high at a lower energy density, while it decreased at a higher energy density.

  12. Solvent effect on the absorption spectra of coumarin 120 in water: A combined quantum mechanical and molecular mechanical study.

    PubMed

    Sakata, Tetsuya; Kawashima, Yukio; Nakano, Haruyuki

    2011-01-07

    The solvent effect on the absorption spectra of coumarin 120 (C120) in water was studied utilizing the combined quantum mechanical∕molecular mechanical (QM∕MM) method. In molecular dynamics (MD) simulation, a new sampling scheme was introduced to provide enough samples for both solute and solvent molecules to obtain the average physical properties of the molecules in solution. We sampled the structure of the solute and solvent molecules separately. First, we executed a QM∕MM MD simulation, where we sampled the solute molecule in solution. Next, we chose random solute structures from this simulation and performed classical MD simulation for each chosen solute structure with its geometry fixed. This new scheme allowed us to sample the solute molecule quantum mechanically and sample many solvent structures classically. Excitation energy calculations using the selected samples were carried out by the generalized multiconfigurational perturbation theory. We succeeded in constructing the absorption spectra and realizing the red shift of the absorption spectra found in polar solvents. To understand the motion of C120 in water, we carried out principal component analysis and found that the motion of the methyl group made the largest contribution and the motion of the amino group the second largest. The solvent effect on the absorption spectrum was studied by decomposing it in two components: the effect from the distortion of the solute molecule and the field effect from the solvent molecules. The solvent effect from the solvent molecules shows large contribution to the solvent shift of the peak of the absorption spectrum, while the solvent effect from the solute molecule shows no contribution. The solvent effect from the solute molecule mainly contributes to the broadening of the absorption spectrum. In the solvent effect, the variation in C-C bond length has the largest contribution on the absorption spectrum from the solute molecule. For the solvent effect on the

  13. Modeling of IR absorption spectra of the mixture CO2-He at moderate and high pressures

    NASA Astrophysics Data System (ADS)

    Golovko, Vladimir F.

    2004-02-01

    The He-broadened spectra of carbon dioxide are calculated within the pressure range 2-800 atm in the absorption regions of the bands v2, v3, and 3v3 that are positioned from 590 to 7020 cm-1. The main difficulty is consideration of the line shape narrowing at relatively high pressures. For Q-branches, this effect is observed at atmospheric conditions and, therefore, it is important for remote sounding of the gas atmosphere. The mixtures of the mentioned gases are well studied in experiments and it can serve as a good test for validating the simulating techniques developing. The line by line method is used with modeling of the single line shape without the conventional interference of lines. The problem is focused on the order and disorder in arrangement of the rotational lines with P-, R-, and Q-branches of vibrational bands. A database CDSD-1000 in the HITRAN format is reformatted with adding supplement four parameters for every entry. The physical meaning of the phenomena known as the line and branch mixing is discussed.

  14. Dielectronic Recombination Of Iron M-shell Ions Motivated By Absorption Features In AGN Spectra

    NASA Astrophysics Data System (ADS)

    Lukic, Dragan; Schnell, M.; Savin, D. W.; Brandau, C.; Schmidt, E. W.; Yu, D.; Bernhardt, D.; Schippers, S.; Müller, A.; Lestinsky, M.; Orlov, D.; Sprenger, F.; Grieser, M.; Repnow, R.; Hoffmann, J.; Wolf, A.

    2006-09-01

    XMM-Newton and Chandra observations of active galactic nuclei (AGN) show spectra rich with X-ray absorption features. These observations have detected a broad unresolved transition array (UTA) between 15-17 Å. This is attributed to inner-shell photoexcitation of M-shell iron ions. Modeling these UTA features is currently limited by uncertainties in the low-temperature dielectronic recombination (DR) data for M-shell iron. In order to resolve this issue, and to provide reliable iron M-shell DR data for plasma modeling, we are carrying out a series of laboratory measurements using the heavy-ion Test Storage Ring (TSR) at the Max-Plank-Institute for Nuclear Physics in Heidelberg, Germany. We use the DR data obtained at TSR, to calculate rate coefficients for plasma modeling. We are also providing our data to atomic theorist to benchmark their DR calculations. Here we report our recent experimental results for DR for several iron M-shell ions and plans for future work. This work has been supported in part by NASA, the German Federal Ministry for Education and Research, and the German Research Council

  15. Free-energy predictions and absorption spectra calculations for supramolecular nanocarriers and their photoactive cargo.

    PubMed

    Pietropaolo, Adriana; Tang, Sicheng; Raymo, Françisco M

    2017-04-13

    We reconstructed the free-energy landscape for supramolecular nanoparticles of amphiphilic methacrylated-based co-polymers. Their self-assembly in aqueous solution and encapsulation of borondipyrromethene (BODIPY) derivatives were enforced through atomistic free-energy simulations. The BODIPY binding modes detected in each of the free-energy basins were validated through a comparison of theoretical absorption spectra, calculated at the TD-DFT level, to their experimental counterparts. The nanoparticle distribution is controlled within a thermodynamic regime, with free-energy barriers approaching 8 kcal mol(-1), enabling the existence of different-sized nanoparticles in aqueous solution at room temperature. Two types of supramolecular morphologies were identified. One is compact and spherical in shape and the other is large and donut-like, with the former more stable than the latter by 4 kcal mol(-1). The morphology of the supramolecular host affects the binding mode of the BODIPY guests. Stacked BODIPY aggregates are encapsulated in the spherical nanocarriers, whereas isolated chromophores associate with the donut-shaped assemblies.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  17. Calibration-free absolute quantification of optical absorption coefficients using acoustic spectra in 3D photoacoustic microscopy of biological tissue.

    PubMed

    Guo, Zijian; Hu, Song; Wang, Lihong V

    2010-06-15

    Optical absorption is closely associated with many physiological important parameters, such as the concentration and oxygen saturation of hemoglobin, and it can be used to quantify the concentrations of nonfluorescent molecules. We propose a method to use acoustic spectra of photoacoustic signals to quantify the absolute optical absorption. This method is self-calibrating and thus insensitive to variations in the optical fluence. Factors such as system bandwidth and acoustic attenuation can affect the quantification but can be canceled by dividing the acoustic spectra measured at two optical wavelengths. Using optical-resolution photoacoustic microscopy, we quantified the absolute optical absorption of black ink samples with various concentrations. We also quantified both the concentration and oxygen saturation of hemoglobin in a live mouse in absolute units.

  18. Bethe-Salpeter calculation of optical-absorption spectra of In2O3 and Ga2O3

    NASA Astrophysics Data System (ADS)

    Varley, Joel B.; Schleife, André

    2015-02-01

    Transparent conducting oxides keep attracting strong scientific interest not only due to their promising potential for ‘transparent electronics’ applications but also due to their intriguing optical absorption characteristics. Materials such as In2O3 and Ga2O3 have complicated unit cells and, consequently, are interesting systems for studying the physics of excitons and anisotropy of optical absorption. Since currently no experimental data is available, for instance, for their dielectric functions across a large photon-energy range, we employ modern first-principles computational approaches based on many-body perturbation theory to provide theoretical-spectroscopy results. Using the Bethe-Salpeter framework, we compute dielectric functions and we compare to spectra computed without excitonic effects. We find that the electron-hole interaction strongly modifies the spectra and we discuss the anisotropy of optical absorption that we find for Ga2O3 in relation to existing theoretical and experimental data.

  19. Simulation studies for operating electron beam ion trap at very low energy for disentangling edge plasma spectra

    SciTech Connect

    Jin Xuelong; Fei Zejie; Xiao Jun; Lu Di; Hutton, Roger; Zou Yaming

    2012-07-15

    Electron beam ion traps (EBITs) are very useful tools for disentanglement studies of atomic processes in plasmas. In order to assist studies on edge plasma spectroscopic diagnostics, a very low energy EBIT, SH-PermEBIT, has been set up at the Shanghai EBIT lab. In this work, simulation studies for factors which hinder an EBIT to operate at very low electron energies were made based on the Tricomp (Field Precision) codes. Longitudinal, transversal, and total kinetic energy distributions were analyzed for all the electron trajectories. Influences from the electron current and electron energy on the energy depression caused by the space charge are discussed. The simulation results show that although the energy depression is most serious along the center of the electron beam, the electrons in the outer part of the beam are more likely to be lost when an EBIT is running at very low energy. Using the simulation results to guide us, we successfully managed to reach the minimum electron beam energy of 60 eV with a beam transmission above 57% for the SH-PermEBIT. Ar and W spectra were measured from the SH-PermEBIT at the apparent electron beam energies (read from the voltage difference between the electron gun cathode and the central drift tube) of 60 eV and 1200 eV, respectively. The spectra are shown in this paper.

  20. An X-ray Absorption Edge Detector for High-Resolution Measurement of Undulator Effective K-Parameter

    SciTech Connect

    Yang, B.; Galayda, J.N.; /SLAC

    2007-03-07

    The spectrum of angle-integrated undulator radiation displays a sharp edge at every harmonic photon energy. A technique utilizing this feature to measure minute changes in K-parameters of an undulator in a free-electron laser has been proposed. To date, this technique requires the use of crystal monochromators as bandpass filters whose energy centroid depends on the incident angle of the x-ray beam. In this work we propose to use the absorption edge of an appropriate element as an energy-selective detector whose response is truly independent of the angle of the x-ray beam, and hence independent of electron beam direction and emittance. We will discuss the basic design concept of the detection system and illustrate its projected performance with computer simulations.

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  2. Chemical analysis for optimal synthesis of ferrihydrite-modified diatomite using soft X-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

    2009-12-01

    Effects of process parameters such as concentrations of FeCl2, NaOH, and drying temperature on the formation mechanism and chemical characteristics of ferrihydrite-modified diatomite are studied by using X-ray absorption near-edge structure spectroscopy. The spectra were recorded in total electron yield mode and/or fluorescence yield mode to investigate the chemical nature of Fe and Si on the surface and/or in the bulk of ferrihydrite-modified diatomite, respectively. It was found that only the surface SiO2 was partially dissolved in the NaOH solution with stirring and heating, whereas the bulk of diatomite seemed to be preserved. The dissolved Si was incorporated into the structure of ferrihydrite to form the 2-line Si-containing ferrihydrite on the surface of diatomite. The crystalline degree of ferrihydrite increased with the increasing FeCl2 concentration and the Brunauer-Emmett-Teller specific surface area of ferrihydrite-modified diatomite decreased with the increasing FeCl2 concentration. The crystalline degree of ferrihydrite decreased with the increase of NaOH concentration. The high temperature calcination caused an energy shift in the Si L-edge spectra to the high energy side and a transformation of Si-containing ferrihydrite to crystallized hematite might occur when ferrihydrite-modified diatomite is calcined at 900°C. In this study, the optimal synthesis conditions for the ferrihydrite-modified diatomite with the least crystalline Si-containing ferrihydrite and the highest surface area were found to be as the follows: 0.5 M FeCl2 solution, 6 M NaOH solution and drying temperature of 50°C.

  3. Analysis of Atmospheric Trace Constituents from High Resolution Infrared Balloon-Borne and Ground-Based Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Rinsland, C. P.; Blatherwick, R. D.; Murcray, F. H.; Murcray, D. G.

    1991-01-01

    Recent results and ongoing studies of high resolution solar absorption spectra will be presented. The analysis of these spectra is aimed at the identification and quantification of trace constituents important in atmospheric chemistry of the stratosphere and upper troposphere. Analysis of balloon-borne and ground-based spectra obtained at 0.0025/ cm covering the 700-2200/ cm interval will be presented. Results from ground-based 0.02/ cm solar spectra, from several locations such as Denver, South Pole, M. Loa, and New Zealand will also be shown. The 0.0025/ cm spectra show many new spectroscopic features. The analysis of these spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of trace constituents quantification. The combination of the recent balloon flights, with earlier flights data since 1978 at 0.02/ cm resolution, provides trends analysis of several stratospheric trace species. Results for COF2, F22, SF6, and other species will be presented. Analysis of several ground-based solar spectra provides trends for HCl, HF and other species. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra will be presented. These are extended for the analysis of the ground-based spectra to be obtained by the high resolution interferometers of the Network for Detection of Stratospheric Change (NDSC). Progress or the University of Denver studies for the NDSC will be presented. This will include intercomparison of solar spectra and trace gases retrievals obtained from simultaneous scans by the high resolution (0.0025/ cm) interferometers of BRUKER and BOMEM.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  5. Density functional calculations of the vibronic structure of electronic absorption spectra.

    PubMed

    Dierksen, Marc; Grimme, Stefan

    2004-02-22

    Calculations of the vibronic structure in electronic spectra of large organic molecules based on density functional methods are presented. The geometries of the excited states are obtained from time-dependent density functional (TDDFT) calculations employing the B3LYP hybrid functional. The vibrational functions and transition dipole moment derivatives are calculated within the harmonic approximation by finite difference of analytical gradients and the transition dipole moment, respectively. Normal mode mixing is taken into account by the Duschinsky transformation. The vibronic structure of strongly dipole-allowed transitions is calculated within the Franck-Condon approximation. Weakly dipole-allowed and dipole-forbidden transitions are treated within the Franck-Condon-Herzberg-Teller and Herzberg-Teller approximation, respectively. The absorption spectra of several organic pi systems (anthracene, pentacene, pyrene, octatetraene, styrene, azulene, phenoxyl) are calculated and compared with experimental data. For dipole-allowed transitions in general a very good agreement between theory and experiment is obtained. This indicates the good quality of the optimized geometries and harmonic force fields. Larger errors are found for the weakly dipole-allowed S0 --> S1 transition of pyrene which can tentatively be assigned to TDDFT errors for the relative energies of excited states close to the target state. The weak bands of azulene and phenoxyl are very well described within the Franck-Condon approximation which can be explained by the large energy gap (>1.2 eV) to higher-lying excited states leading to small vibronic couplings. Once corrections are made for the errors in the theoretical 0-0 transition energies, the TDDFT approach to calculate vibronic structure seems to outperform both widely used ab initio methods based on configuration interaction singles or complete active space self-consistent field wave functions and semiempirical treatments regarding accuracy

  6. Analysis of Gain and Absorption Spectra of Gallium Nitride-based Laser Diodes

    NASA Astrophysics Data System (ADS)

    Melo, Thiago

    Laser diodes (LDs) based on the III-Nitride material system, (Al,In,Ga)N, stand to satisfy a number of application needs, and their huge market segment has been further growing with the use of LDs for full color laser projection. All commercially available GaN-based devices are based on the conventional c-plane (polar) orientation of this material. However, strong polarization fields caused by strained quantum-well (QW) layers on c-plane induce the quantum-confined Stark effect (QCSE), which leads to reduced radiative recombination rate and are aggravated when more indium is added into the QW(s) in order to achieve longer wavelengths. A promising solution for this is the use of nonpolar and semipolar crystal growth orientations. Elimination or mitigation of polarization-related fields within the QWs grown along these novel orientations is observed and one expects increased radiative recombination rate and stabilization of the wavelength emission with respect to the injection current. In order to have more insights on the advantages of using the novel crystal orientations of the III-Nitride material system, we compare the gain of LD structures fabricated from c-plane, nonpolar and semipolar GaN substrates. Using thesegmented contact method, single-pass gain spectra of LD epitaxial structures at wafer level are compared for the different crystal orientations as well as the single-pass absorption coefficient spectrum of the active region material and its dependence on reversed bias. Experimental gain spectra under continuous-wave (CW) operation of actual industry LDs fabricated from c-plane and nonpolar/semipolar GaN-based materials emitting wavelengths in the visible are then presented, using the Hakki-Paoli technique at high resolution. Measurements of the transparency current density, total losses and differential modal gain curves up to threshold are analyzed and compared between nonpolar/semipolar and c-plane LDs in violet and blue spectral regions regions. In a

  7. Collison-induced rototranslational absorption spectra of H2-He pairs at temperatures from 40 to 3000 K

    NASA Technical Reports Server (NTRS)

    Borysow, Jacek; Frommhold, Lothar; Birnbaum, George

    1988-01-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H2-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K.

  8. Collison-induced rototranslational absorption spectra of H/sub 2/-He pairs at temperatures from 40 to 3000 K

    SciTech Connect

    Borysow, J.; Frommhold, L.; Birnbaum, G.

    1988-03-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H/sub 2/-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K. 28 references.

  9. Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes.

    PubMed

    Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya

    2012-04-01

    Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

  10. Electronic absorption spectra of rare earth (III) species in NaCl-2CsCl eutectic based melts

    NASA Astrophysics Data System (ADS)

    Volkovich, V. A.; Ivanov, A. B.; Yakimov, S. M.; Tsarevskii, D. V.; Golovanova, O. A.; Sukhikh, V. V.; Griffiths, T. R.

    2016-09-01

    Electronic absorption spectra of ions of trivalent rare earth elements were measured in the melts based on NaCl-2CsCl eutectic in the wavelength ranges of 190-1350 and 1450-1700 nm. The measurements were performed at 550-850 °C. The EAS of Y, La, Ce and Lu containing melts have no absorption bands in the studied regions. For the remaining REEs (Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) the absorption bands in the EAS were assigned to the corresponding f-f electron transitions. The Stark effect was observed for Yb(III) F5/2 excited state. Increasing temperature leads to decreasing intensity of the absorption bands, except for the bands resulting from hypersensitive transitions. Beer's law was confirmed up to 0.4 M solutions of REE.

  11. Solvent dependence of two-photon absorption spectra of the enhanced green fluorescent protein (eGFP) chromophore

    NASA Astrophysics Data System (ADS)

    Hosoi, Haruko; Tayama, Ryo; Takeuchi, Satoshi; Tahara, Tahei

    2015-06-01

    Two-photon absorption spectra of 4‧-hydroxybenzylidene-2,3-dimethylimidazolinone, a model chromophore of enhanced green fluorescent protein (eGFP), were measured in various solvents. The two-photon absorption band of its anionic form is markedly blue-shifted from the corresponding one-photon absorption band in all solvents. Moreover, the magnitude of the blue shift varies largely depending on the solvent, which does not accord with the assignment of the two-photon absorption band to the transitions to the vibrationally excited S1 state. Our finding is readily rationalized by considering overlapping contributions of the S1 ← S0 and S2 ← S0 transitions, suggesting the involvement of the S2 state also in two-photon fluorescence of eGFP.

  12. Electronic Absorption Spectra of Tetrapyrrole-Based Pigments via TD-DFT: A Reduced Orbital Space Study.

    PubMed

    Shrestha, Kushal; Virgil, Kyle A; Jakubikova, Elena

    2016-07-28

    Tetrapyrrole-based pigments play a crucial role in photosynthesis as principal light absorbers in light-harvesting chemical systems. As such, accurate theoretical descriptions of the electronic absorption spectra of these pigments will aid in the proper description and understanding of the overall photophysics of photosynthesis. In this work, time-dependent density functional theory (TD-DFT) at the CAM-B3LYP/6-31G* level of theory is employed to produce the theoretical absorption spectra of several tetrapyrrole-based pigments. However, the application of TD-DFT to large systems with several hundreds of atoms can become computationally prohibitive. Therefore, in this study, TD-DFT calculations with reduced orbital spaces (ROSs) that exclude portions of occupied and virtual orbitals are pursued as a viable, computationally cost-effective alternative to conventional TD-DFT calculations. The effects of reducing orbital space size on theoretical spectra are qualitatively and quantitatively described, and both conventional and ROS results are benchmarked against experimental absorption spectra of various tetrapyrrole-based pigments. The orbital reduction approach is also applied to a large natural pigment assembly that comprises the principal light-absorbing component of the reaction center in purple bacteria. Overall, we find that TD-DFT calculations with proper and judicious orbital space reductions can adequately reproduce conventional, full orbital space, TD-DFT results of all pigments studied in this work.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    It is very important to determine electron transition energies (Etr) 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 (Etr) between the anions and cations, Fe2+ and Fe3+ at the (A) and [B] sites and Ni2+ at the [B] sites for the (A)[B]2O4 spinel ferrite samples CoxNi0.7-xFe2.3O4 (0.0≤x≤0.3), CrxNi0.7Fe2.3-xO4 (0.0≤x≤0.3) and Fe3O4. 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.

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

    PubMed

    Fransson, Thomas; Coriani, Sonia; Christiansen, Ove; Norman, Patrick

    2013-03-28

    Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this

  15. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations.

    PubMed

    Ge, Qinghui; Mao, Yuezhi; White, Alec F; Epifanovsky, Evgeny; Closser, Kristina D; Head-Gordon, Martin

    2017-01-28

    Simulations of the n = 2 absorption spectra of HeN (N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. A detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.

  16. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations

    NASA Astrophysics Data System (ADS)

    Ge, Qinghui; Mao, Yuezhi; White, Alec F.; Epifanovsky, Evgeny; Closser, Kristina D.; Head-Gordon, Martin

    2017-01-01

    Simulations of the n = 2 absorption spectra of HeN (N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. A detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.

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

    SciTech Connect

    Fransson, Thomas; Norman, Patrick; Coriani, Sonia; Christiansen, Ove

    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 {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this

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

    SciTech Connect

    Laloum, D.; Printemps, T.; Bleuet, P.; Lorut, F.

    2015-01-15

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

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

    PubMed

    Laloum, D; Printemps, T; Lorut, F; Bleuet, P

    2015-01-01

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

  20. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    PubMed Central

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  1. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    NASA Astrophysics Data System (ADS)

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-07-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics.

  2. Near-edge X-ray absorption spectroscopy signature of image potential states in multilayer epitaxial graphene

    NASA Astrophysics Data System (ADS)

    Coelho, P. M.; dos Reis, D. D.; Matos, M. J. S.; Mendes-de-Sa, T. G.; Goncalves, A. M. B.; Lacerda, R. G.; Malachias, A.; Magalhaes-Paniago, R.

    2016-02-01

    Single layer behavior in multilayer epitaxial graphene has been a matter of intense investigation. This is due to the layer decoupling that occurs during growth of graphene on some types of substrates, such as carbon-terminated silicon carbide. We show here that near-edge X-ray absorption spectroscopy can be used to observe the signature of this decoupling. To this end, samples of multilayer graphene from silicon carbide sublimation were grown with different degrees of decoupling. Raman spectroscopy was used to infer the degree of structural decoupling. X-ray grazing-incidence diffraction and scanning tunneling microscopy showed that growth initiates with the presence of bilayer graphene commensurate structures, while layer decoupling is associated to the formation of incommensurate structures observed for longer sublimation time. Near-edge X-ray absorption spectroscopy was used to probe the electronic states above the Fermi energy. Besides the σ* and π* empty states, image potential states are observed and show a clear change of intensity as a function of incident angle. These image potential states evolve from a graphite- to graphene-like behavior as a function of growth time and can be used to infer the degree of structural coupling among layers.

  3. Temperature dependence and annealing effects of absorption edges for selenium quantum dots formed by ion implantation in silica glass

    SciTech Connect

    Ueda, A.; Wu, M.; Mu, R.

    1998-12-31

    The authors have fabricated Se nanoparticles in silica substrates by ion implantation followed by thermal annealing up to 1000 C, and studied the Se nanoparticle formation by optical absorption spectroscopy, Rutherford backscattering spectrometry, X-ray diffraction, and transmission electron microscopy. The sample with the highest dose (1 {times} 10{sup 17} ions/cm{sup 2}) showed the nanoparticle formation during the ion implantation, while the lower dose samples (1 and 3 {times} 10{sup 16} ions/cm{sup 2}) required thermal treatment to obtain nano-sized particles. The Se nanoparticles in silica were found to be amorphous. After thermal annealing, the particle doses approached the value of bulk after thermal annealing. The temperature dependent absorption spectra were also measured for this system in a temperature range from 15 to 300 K.

  4. Electronic structure and optical absorption spectra of CdSe covered with ZnSe and ZnS epilayers

    NASA Astrophysics Data System (ADS)

    Yun, So Jeong; Lee, Geunsik; Kim, Jai Sam; Shin, Seung Koo; Yoon, Young-Gui

    2006-02-01

    Using the first-principles methods we compute the electronic structure and the absorption spectra for a wurtzite CdSe (0001) slab covered with zincblende ZnSe and ZnS epilayers. For each structure we compute the DOS and the imaginary part of the dielectric function. We find that the semiconductor passivation shifts the 'near Fermi-level' states of the bare CdSe slab down to lower energy levels. The migration suggests the decrease of surface effects and energy loss. We observe the substantial reduction of the abnormal peaks in the absorption spectra of the bare CdSe slab, which seems to be a consequence of the DOS migration. This is consistent with the experimental results that a proper passivation enhance the luminescence efficiency. We also study the case that the epilayer surface is terminated with PH 3 and find the PH 3 passivation also reduces the surface state to some extent.

  5. The structure of the absorption spectra of the quasars Q 0420-388 and Q 1101-264

    NASA Astrophysics Data System (ADS)

    Chernomordik, V. V.

    1988-08-01

    The spectra of the quasars Q 0420-388 and Q 1101-264 are studied in the framework of the shock-wave model of the Lyman-alpha forest in the spectra of distant quasars, in which the origin of Lyman-alpha absorption lines is related to absorption zones in the shells of metagalactic shock waves. It is shown that more that 50 percent of the narrow Lyman-alpha abosrption lines are components of doublets, or pairs of nearby lines with the same equivalent widths. This is in good agreement with the predictions of the shock-wave model. The expected H I column density distribution of the Lyman-alpha lines is calculated and is found to be in agreement with the findings of Atwood et al. (1985).

  6. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    SciTech Connect

    Zhao, Shijun; Zhang, Shen; Kang, Wei; Li, Zi; Zhang, Ping; He, Xian-Tu

    2015-06-15

    Principal Hugoniot and K-shell X-ray absorption spectra of warm dense KCl are calculated using the first-principles molecular dynamics (FPMD) method. Evolution of electronic structures as well as the influence of the approximate description of ionization on pressure (caused by the underestimation of the energy gap between conduction bands and valence bands) in the first-principles method are illustrated by the calculation. It is shown that approximate description of ionization in FPMD has small influence on Hugoniot pressure due to mutual compensation of electronic kinetic pressure and virial pressure. The calculation of X-ray absorption spectra shows that the band gap of KCl persists after the pressure ionization of the 3p electrons of Cl and K taking place at lower energy, which provides a detailed understanding to the evolution of electronic structures of warm dense matter.

  7. Using high-resolution laboratory and ground-based solar spectra to assess CH4 absorption coefficient calculations

    NASA Astrophysics Data System (ADS)

    Mendonca, J.; Strong, K.; Sung, K.; Devi, V. M.; Toon, G. C.; Wunch, D.; Franklin, J. E.

    2017-03-01

    A quadratic-speed-dependent Voigt line shape (qSDV) with line mixing (qSDV+LM), together with spectroscopic line parameters from Devi et al. [1,2] for the 2v3 band of CH4, was used to retrieve total columns of CH4 from atmospheric solar absorption spectra. The qSDV line shape (Tran et al., 2013) [3] with line mixing (Lévy et al., 1992) [4] was implemented into the forward model of GFIT (the retrieval algorithm that is at the heart of the GGG software (Wunch et al., 2015) [5]) to calculate CH4 absorption coefficients. High-resolution laboratory spectra of CH4 were used to assess absorption coefficients calculated using a Voigt line shape and spectroscopic parameters from the atm line list (Toon, 2014) [6]. The same laboratory spectra were used to test absorption coefficients calculated using the qSDV+LM line shape with spectroscopic line parameters from Devi et al. [1,2] for the 2v3 band of CH4 and a Voigt line shape for lines that don't belong to the 2v3 band. The spectral line list for lines that don't belong to the 2v3 band is an amalgamation of multiple spectral line lists. We found that for the P, Q, and R branches of the 2v3 band, the qSDV+LM simulated the laboratory spectra better than the Voigt line shape. The qSDV+LM was also used in the spectral fitting of high-resolution solar absorption spectra from four ground-based remote sensing sites and compared to spectra fitted with a Voigt line shape. The average root mean square (RMS) residual for 131,124 solar absorption spectra fitted with absorption coefficients calculated using the qSDV+LM for the 2v3 band of CH4 and the new spectral line list for lines for lines that don't belong to the 2v3 band, was reduced in the P, Q, and R branches by 5%, 13%, and 3%, respectively when compared with spectra fitted using a Voigt line shape and the atm line list. We found that the average total column of CH4 retrieved from these 131,124 spectra, with the qSDV+LM was 1.1±0.3% higher than the retrievals performed using a

  8. Simulation of FREE→FREE Absorption Spectra and the Calculation of Interaction Potentials for Alkali-Rare Gas Atom Pairs

    NASA Astrophysics Data System (ADS)

    Hewitt, J. Darby; Spinka, Thomas M.; Readle, Jason. D.; Eden, J. Gary

    2013-06-01

    We have simulated free→free (X^2Σ^+_{1/2}→B^2Σ^+_{1/2}) absorption spectra for alkali-rare gas pairs. By comparing simulation results with experimental data, we have been able to iteratively determine the form for the B^2Σ^+_{1/2} interaction potential for the system for a range in internuclear separation of 1.5-20 Å. Simulation methods will be presented, as will our results pertaining to Cs-Ar.

  9. Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra

    SciTech Connect

    Meyer, Wilfried; Frommhold, Lothar

    2015-09-21

    Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He–Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D{sub 7} is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

  10. Polarized absorption spectra of aromatic radicals in stretched polymer film. 3. Radical ions of acridine and phenazine

    SciTech Connect

    Sekigucki, K.; Hiratsuka, H.; Tanizaki, Y.; Hatano, Y.

    1980-02-21

    Radical anions and cations of acridine and phenazine have been prepared in polymer film by ..gamma..-ray irradiation at 77 K. For the preparation of radical anions the sample was incorporated into polyethylene film by sec-butylamine, while for radical cations poly(vinyl chloride) film and sec-butyl chloride were used. Polarized absorption spectra of these radical ions have been measured in stretched polymer film and analyzed qualitatively in terms of molecular orbital calculations.

  11. Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra.

    PubMed

    Meyer, Wilfried; Frommhold, Lothar

    2015-09-21

    Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He-Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D7 is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

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

    DTIC Science & Technology

    2016-06-03

    of Arsenic- Water Complexes Using Density Functional Theory June 3, 2016 Approved for public release; distribution is unlimited. L. Huang S.g...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic- Water Complexes Using... water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  14. Research program in nuclear and solid state physics. [including pion absorption spectra and muon spin precession

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The survey of negative pion absorption reactions on light and medium nuclei was continued. Muon spin precession was studied using an iron target. An impulse approximation model of the pion absorption process implied that the ion will absorb almost exclusively on nucleon pairs, single nucleon absorption being suppressed by energy and momentum conservation requirements. For measurements on both paramagnetic and ferromagnetic iron, the external magnetic field was supplied by a large C-type electromagnet carrying a current of about 100 amperes.

  15. Application of Video Spectral Comparator (absorption spectra) for establishing the chronological order of intersecting printed strokes and writing pen strokes.

    PubMed

    Kaur, Ridamjeet; Saini, Komal; Sood, N C

    2013-06-01

    The sequence of intersecting strokes of laser printers (black, blue, red and green) and typewriter ink (black) with the strokes of gel pen ink, ballpoint pen ink and fountain pen ink (black, blue, red and green) has been determined by studying their absorption spectra. The absorption spectra have been generated for each of the two pure inks (i.e. A and B) and points of their intersections (i.e. A over B and B over A) by using Video Spectral Comparator (VSC-2000-HR). The study was carried out with an assumption that the peak characteristics of spectra from the point of intersection should correspond to the peak characteristics of pure ink which was executed later. It was observed that the absorption spectrum of intersection corresponds with either the laser printer or the typewriter ink stroke, whether these strokes were executed earlier or later than the writing instrument strokes. As the results obtained from the study were negative, the FDEs are advised against the practice of this technique in the examination of the sequence of intersecting strokes for these specified inks.

  16. pH-Induced changes in electronic absorption and fluorescence spectra of phenazine derivatives

    NASA Astrophysics Data System (ADS)

    Ryazanova, O. A.; Voloshin, I. M.; Makitruk, V. L.; Zozulya, V. N.; Karachevtsev, V. A.

    2007-04-01

    The visible electronic absorption and fluorescence spectra as well as fluorescence polarization degrees of imidazo-[4,5-d]-phenazine (F1), 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), 1,2,3-triazole-[4,5-d]-phenazine (F4) and their glycosides, imidazo-[4,5-d]-phenazine-N1-β- D-ribofuranoside (F1rib), 1,2,3-triazole-[4,5-d]-phenazine-N1-β- D-glucopyranoside (F4gl), were investigated in aqueous buffered solutions over the pH range of 0-12, where the spectral transformations were found to be reversible. The effects of protonation and deprotonation on spectral properties of these dyes were studied. We have determined the ranges of pH, where individual ionic species are predominant. In aqueous buffered solutions the fluorescence was found only for neutral species of F1, F1rib, F2, and F4gl dyes, whereas for the ionic forms of these dyes, as well as for F3 and F4 ones, the fluorescence has not been detected. The concentrational deprotonation p Ka values were evaluated from experimental data. It was shown that donor-acceptor properties of the substituent group in the second position of the pentagonal ring substantially affect the values of the deprotonation constants and the character of protonation for chromophore. The substitution of a hydrogen atom in the NH-group by the sugar residue blocks the formation of the anionic species, and results in enhancement of the dye emission intensity. The steep emission dependence for F1 and F1rib over pH range of 0-7 with intensities ratio of IpH 7/ IpH 1 = 60 allows us to propose them as possible indicator dyes in luminescence based pH sensors for investigation of processes accompanied by acidification, e.g. as gastric pH-sensors. A comparative analysis of the studied dyes has shown that F4gl is the most promising compound to be used as a fluorescent probe for investigation of molecular hybridization of nucleic acids.

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

    SciTech Connect

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

    PubMed

    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.

  19. Electric field effect on the nonlinear and linear intersubband absorption spectra in CdTe/ZnTe spherical quantum dot

    NASA Astrophysics Data System (ADS)

    Kostić, Radmila; Stojanović, Dušanka

    2012-01-01

    Linear and nonlinear absorption spectra of neutral (D0) hydrogenic impurity located at the center of the CdTe/ZnTe spherical quantum dot (QD) were investigated after assuming a spherically symmetric confining potential of finite depth. Calculations were performed under the effective mass approximation on the basis of exact solution of the Schrödinger and Poisson equations. Eigenfunctions were expressed in terms of the Whittaker and Coulomb wave functions. Results for D0 impurity energies of ground 1s, and excited 2p, 3d, and 2s states strongly depend on QD radius if it does not exceed a few effective Bohr radius. Wave functions and Stark shift energy levels in external electric field were determined from a variational-calculus approach for states labeled m=0. The absorption spectra for intersubband transitions were found to depend strongly on the QD radius. Whether or not the impurity is present, the peak energy of absorption decreases with increasing QD radius. An external electric field increases the transition energy but does not significantly change absorption characteristics.

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Ultraviolet-visible absorption spectra of N-doped TiO2 film deposited on sapphire

    NASA Astrophysics Data System (ADS)

    Park, Jaewon; Lee, Jung-Yup; Cho, Jun-Hyung

    2006-12-01

    The optical-response properties of nitrogen(N)-doped titanium dioxide (TiO2) films are investigated by means of a combination of ultraviolet-visible absorption spectroscopy and first-principles density-functional calculations. The TiO2 films were epitaxially grown on the sapphire substrate by the pulsed laser deposition method. The doping of N atoms was achieved by 70keV of N+ ion implantation, followed by postirradiation heat treatment at 550°C for 2h in air. We find that when 5×1016 (1×1017)Nions/cm2 were implanted into the epitaxially grown TiO2 film, the absorption edge is reproducibly shifted to lower energy by about 0.06 (0.12)eV together with a significant optical absorption extending into the visible-light region. These experimental data can be explained by our calculated band structure of N-doped TiO2, where the bands originating from N 2p states locate above the valence band edge, while the band gap narrowing due to the mixing of N with O 2p states is 0.04eV.

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

    PubMed

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

    2016-06-14

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

  3. Light-induced relaxation of photolyzed carbonmonoxy myoglobin: a temperature-dependent x-ray absorption near-edge structure (XANES) study.

    PubMed

    Arcovito, A; Lamb, D C; Nienhaus, G U; Hazemann, J L; Benfatto, M; Della Longa, S

    2005-04-01

    X-ray absorption near-edge structure (XANES) spectra at the Fe K-edge have been measured and compared on solution samples of horse carbonmonoxy-myoglobin and its photoproducts, prepared by two different photolysis protocols: 1), extended illumination at low temperature (15 K) by white light; and 2), slow-cool from 140 to 10 K at a rate of 0.5 K/min while illuminating the sample with a 532-nm continuous-wave laser source. CO recombination has been followed while increasing the temperature at a rate of 1.2 K/min. After extended illumination at 15 K, a single process is observed, corresponding to CO recombination from a completely photolyzed species with CO bound to the primary docking site (formally B-state, in agreement with previous x-ray diffraction studies). The temperature peak for this single process is approximately 50 K. Using slow-cool illumination, data show a two-state recombination curve, the two temperature peaks being roughly assigned to 50 K and 110 K. These results are in good agreement with previous FTIR studies using temperature-derivative spectroscopy. The XANES spectroscopic markers probe structural differences between the photoproduct induced by extended illumination at 15 K and the photoproduct induced by slow-cool illumination. These differences in the XANES data have been interpreted as due to light-induced Fe-heme relaxation that does not involve CO migration from the B-state. A quantitative description of the unrelaxed and relaxed B-states, including the measurements of the Fe-N(p), Fe-N(His), and Fe-CO distances, and the out-of-plane Fe displacement, has been obtained via a procedure (MXAN) recently developed by us. This work shows that XANES, being able to extract both kinetic and structural parameters in a single experiment, is a powerful tool for structural dynamic studies of proteins.

  4. Low-temperature spin-state transition in LaCoO{sub 3} investigated using resonant x-ray absorption at the Co K edge

    SciTech Connect

    Medarde, M.; Pomjakushina, E.; Conder, K.; Dallera, C.; Grioni, M.; Voigt, J.; Podlesnyak, A.; Neisius, Th.; Tjernberg, O.; Barilo, S. N.

    2006-02-01

    LaCoO{sub 3} displays two broad anomalies in the DC magnetic susceptibility {chi}{sup DC}, occurring, respectively, around 50 K and 500 K. We have investigated the first of them within the 10 Kabsorption spectroscopy (XAS) in the partial fluorescence yield mode. In contrast with previous O K-edge XAS reports, our data show the existence of abrupt changes around 50 K which can be nicely correlated with the anomaly in {chi}{sup DC}. To our knowledge, this is the first time that a clear, quantitative relationship between the temperature dependence of the magnetic susceptibility and that of the XAS spectra is reported. The intensity changes in the preedge region, which are consistent with a transition from a lower to a higher spin state, have been analyzed using a minimal model including the Co 3d and O 2p hybridization in the initial state. The temperature dependence of the Co magnetic moment obtained from the estimated e{sub g} and t{sub 2g} occupations could be satisfactorily reproduced. Also, the decrease of the Co 3d and O 2p hybridization by increasing temperature obtained from this simple model compares favorably with the values estimated from thermal evolution of the crystallographic structure.

  5. Computed and Experimental Absorption Spectra of the Perovskite CH3NH3PbI3.

    PubMed

    Zhu, Xi; Su, Haibin; Marcus, Rudolph A; Michel-Beyerle, Maria E

    2014-09-04

    Electronic structure and light absorption properties of the perovskite CH3NH3PbI3 are investigated by relativistic density functional theory with quasiparticle GW corrections and many-body interactions. The nature of the Wannier exciton is studied by solving the Bethe-Salpeter equation augmented with the analysis of a conceptual hydrogen-like model. The computed absorption spectrum unravels a remarkable absorption "gap" between the first two absorption peaks. This discontinuity is maintained in the calculated tetragonal structure that, however, is not stable at low temperature. Most importantly, the discontinuity is also observed in the experimental absorption spectrum of the orthorhombic single crystal at low temperature (4 K). However, in contrast to the single crystal, in a polycrystalline perovskite film at 5 K the "gap" is filled by a monotonously increasing absorption throughout the visible range. This feature of thin films points to the potential significance of defect absorption for the excellent light harvesting properties of perovskite-based solar cells.

  6. Reactivity of the laccase trinuclear copper active site with dioxygen: An x-ray absorption edge study

    SciTech Connect

    Cole, J.L.; Tan, G.O.; Yang, E.K.; Hodgson, K.O.; Solomon, E.I. )

    1990-03-14

    The multicopper oxidases (laccase, ascorbate oxidase, ceruloplasmin) catalyze the four-electron reduction of dioxygen to water. Laccase contains four Cu atoms: a type 1, a type 2, and a coupled binuclear type 3 center. Low-temperature MCD studies of laccase have demonstrated that the type 2 and type 3 centers comprise a trinuclear Cu cluster site and this model has been supported in a recent x-ray crystal structure of ascorbate oxidase. In the present study, x-ray absorption edge spectroscopy has been used to determine Cu oxidation states following reaction of reduced laccase derivatives with dioxygen, leading to a description of which of the Cu centers is required for reactivity.

  7. Iron K-edge X-ray absorption spectroscopy of the iron-molybdenum cofactor of nitrogenase from Klebsiella pneumoniae.

    PubMed Central

    Arber, J M; Flood, A C; Garner, C D; Gormal, C A; Hasnain, S S; Smith, B E

    1988-01-01

    Iron K-edge X-ray absorption data for the iron-molybdenum cofactor ('FeMoco') from Klebsiella pneumoniae reported here provide the first evidence for long-range structural order in the cofactor [Fe...Fe(Mo) = 0.368 nm in addition to Fe...S = 0.22 nm and Fe...Fe(Mo) = 0.27 nm] and, in contrast with previously published data [Antonio, Teo, Orme-Johnson, Nelson, Groh, Lindahl, Kauzlarich & Averill (1982) J. Am. Chem. Soc. 104, 4703-4705], indicate that most of the iron centres are not co-ordinated to light (oxygen, nitrogen) atoms. This demonstrates that presently available chemical models for FeMoco are inadequate. PMID:3046607

  8. Anisotropy of chemical bonds in collagen molecules studied by X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Lam, Raymond S K; Metzler, Rebecca A; Gilbert, Pupa U P A; Beniash, Elia

    2012-03-16

    Collagen type I fibrils are the major building blocks of connective tissues. Collagen fibrils are anisotropic supramolecular structures, and their orientation can be revealed by polarized light microscopy and vibrational microspectroscopy. We hypothesized that the anisotropy of chemical bonds in the collagen molecules, and hence their orientation, might also be detected by X-ray photoemission electron spectromicroscopy (X-PEEM) and X-ray absorption near-edge structure (XANES) spectroscopy, which use linearly polarized synchrotron light. To test this hypothesis, we analyzed sections of rat-tail tendon, composed of parallel arrays of collagen fibrils. The results clearly indicate that XANES-PEEM is sensitive to collagen fibril orientation and, more specifically, to the orientations of carbonyl and amide bonds in collagen molecules. These data suggest that XANES-PEEM is a promising technique for characterizing the chemical composition and structural organization at the nanoscale of collagen-based connective tissues, including tendons, cartilage, and bone.

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

    SciTech Connect

    Andreeva, M. A.; Repchenko, Yu. L.; Smekhova, A. G.; Dumesnil, K.; Wilhelm, F.; Rogalev, A.

    2015-06-15

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

  10. Electrospun nanofibers of Er{sup 3+}-doped TiO{sub 2} with photocatalytic activity beyond the absorption edge

    SciTech Connect

    Zheng, Yali; Wang, Wenzhong

    2014-02-15

    Er{sup 3+}-doped TiO{sub 2} nanofibers with different Er{sup 3+} contents were prepared via electrospinning and characterized by X-ray diffraction, scanning electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy and photocurrent measurement. Photocatalytic activities of the as-prepared samples were evaluated by the decolorization of methyl orange aqueous solution under simulated solar light irradiation. The results indicated that the photocatalytic activity of Er{sup 3+}-doped TiO{sub 2} nanofibers was much higher than that of the undoped one, and the optimal dosage of Er{sup 3+} at 1 mol% achieved the highest degradation rate. Moreover, the photocatalytic activity of Er{sup 3+}-doped TiO{sub 2} nanofibers under the irradiation of light with the wavelength beyond the absorption edge of TiO{sub 2} was explored by the decolorization of a dye, rhodamine B and the photodegradation of a typical colorless pollutant, phenol. The results further revealed the mechanism of the enhanced photocatalytic activity through Er{sup 3+} doping in TiO{sub 2} nanofibers. - Graphical abstract: Display Omitted - Highlights: ●Er{sup 3+}:TiO{sub 2} nanofibers with different Er{sup 3+} contents were prepared via electrospinning. ●The photocatalytic activity of Er{sup 3+}:TiO{sub 2} was much higher than that of undoped one. ●Er{sup 3+}:TiO{sub 2} could be activated by the light with wavelength beyond the absorption edge.

  11. Surface Structure and Chemical Switching of Thioctic Acid Adsorbed on Au(111) as Observed Using Near-Edge X-ray Absorption Fine Structure

    SciTech Connect

    Meulenberg, R W; van Buuren, T; Vance, A L; Terminello, L J; Willey, T M; Bostedt, C; Fadley, C S

    2004-01-06

    Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl-chain with four CH{sub 2} units, and a carboxyl termination. Self-assembled monolayer (SAM) films of thioctic acid adsorbed on Au(111) have been investigated with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS) to determine film quality, bonding and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkyl-thiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38{sup o} from the surface normal. Slight dichroism in other features indicates alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66{sup o} from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules.

  12. Pressure Induced Phase Transition in PbTiO3 Studied by X-ray Absorption Spectroscopy at the Ti K edge

    SciTech Connect

    Dhaussy, A. C.; Marinel, S.; Veres, A.; Jaouen, N.; Itie, J. P.; Rogalev, A.

    2007-01-19

    The Ti-K edge X-ray Absorption Near Edge Structure (XANES) for CaTiO3 and PbTiO3 have been measured under high pressure in a diamond anvil cell at room temperature. Despite the huge absorption from the diamond cell and the sample high quality XANES allows us to observe that in CaTiO3 no change occurs when applying pressure, at the opposite of PbTiO3 in which the pre-edge features vary strongly. It allows studying the phase transition from ferroelectric to paraelectric phase in PbTiO3 from the local point of view. Under pressure the change in intensity of the pre-edge indicates qualitatively that the Ti atom is moving toward the centre of the oxygen octahedron along the c-axis.

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

  14. Cerium valence in cerium-exchanged Preyssler`s heteropolyanion through x-ray absorption near-edge structure

    SciTech Connect

    Antonio, M.R.; Soderholm, L.

    1994-12-21

    The sodium ion in the heteropolytungstate known as the Preyssler anion, [NaP{sub 5}W{sub 30}O{sub 110}]{sup 14{minus}}, was exchanged with cerium from aqueous solutions of ammonium ceric nitrate, [NH{sub 4}]{sub 2}Ce{sup IV}(NO{sub 3}){sub 6}, as described by Creaser et al. The valence of cerium in this heteropolyanion was determined through Ce L-edge XANES, X-ray absorption near-edge structure. The XANES results demonstrate that cerium is trivalent in the Ce-exchanged Preyssler heteropolyanion in the solid state and in aqueous solution (1 M H{sub 2}SO{sub 4}) at rest potential and after constant-potential, bulk electrolysis at-0.55 V vs SCE. The encapsulated sodium ion of the Preyssler anion was shown to be directly exchangeable with Ce{sup III} by prolonged (48 h), high temperature (165 {degrees}C) aqueous treatments with either Ce(NO{sub 3}){sub 3}{lg_bullet}6H{sub 2}O or CeCl{sub 3}{lg_bullet}7H{sub 2}O in Teflon-lined pressure vessels.

  15. Fundamental absorption edges in heteroepitaxial YBiO3 thin films

    NASA Astrophysics Data System (ADS)

    Jenderka, Marcus; Richter, Steffen; Lorenz, Michael; Grundmann, Marius

    2016-09-01

    The dielectric function of heteroepitaxial YBiO3 grown on a-Al2O3 single crystals via pulsed laser deposition is determined in the spectral range from 0.03 eV to 4.5 eV by a simultaneous modeling of the spectroscopic ellipsometry and optical transmission data of YBiO3 films of different thicknesses. The (111)-oriented YBiO3 films are nominally unstrained and crystallize in a defective fluorite-type structure with a F m 3 ¯ m space group. From the calculated absorption spectrum, a direct electronic bandgap energy of 3.6(1) eV and the signature of an indirect electronic transition around 0.5 eV are obtained. These values provide necessary experimental feedback to previous conflicting electronic band structure calculations predicting either a topologically trivial or a non-trivial insulating ground state in YBiO3.

  16. Franck-Condon analysis of the S0 --> T1 absorption and phosphorescence spectra of biphenyl and bridged derivatives

    NASA Astrophysics Data System (ADS)

    Negri, Fabrizia; Zgierski, Marek Z.

    1992-11-01

    The equilibrium geometry and the vibrational force field of the ground and the lowest triplet electronic states of biphenyl and three bridged derivatives-biphenylene, fluorene and phenanthrene-are computed by using an updated version of the QCFF/PI (Quantum Chemical Force Field/π electron) Hamiltonian. The displacement parameters between T1 and S0 are obtained and used to model the S0→T1 absorption and the phosphorescence spectra. The calculated Franck-Condon envelopes are found to be in excellent agreement with the vibrational structure of the observed spectra. The common features of the phosphorescence spectra of biphenyl and fluorene are related to the same orbital nature of the lowest triplet state. The observed asymmetry between the phosphorescence and singlet-triplet absorption spectra of biphenyl is reproduced when the twisted equilibrium geometry of S0 is considered. It is shown that evidence of the nonplanarity of the ground state of biphenyl is manifested by the lower intensity of the band observed in the phosphorescence at 747 cm-1 with respect to the intensity of the same band in fluorene. The increased vibrational activity calculated in the lower frequency region for biphenylene and phenanthrene agrees with the observed spectra and reflects the different orbital nature of the lowest triplet state of the two strongly perturbed bridged derivatives with respect to biphenyl and fluorene. From the analysis of the computed vibrational frequencies, it is suggested that the false origin of the symmetry forbidden phosphorescence of biphenylene is due to the lowest out-of-plane mode of au symmetry.

  17. Auger electron and photoabsorption spectra of glycine in the vicinity of the oxygen K-edge measured with an X-FEL

    NASA Astrophysics Data System (ADS)

    Sanchez-Gonzalez, A.; Barillot, T. R.; Squibb, R. J.; Kolorenč, P.; Agaker, M.; Averbukh, V.; Bearpark, M. J.; Bostedt, C.; Bozek, J. D.; Bruce, S.; Carron Montero, S.; Coffee, R. N.; Cooper, B.; Cryan, J. P.; Dong, M.; Eland, J. H. D.; Fang, L.; Fukuzawa, H.; Guehr, M.; Ilchen, M.; Johnsson, A. S.; Liekhus-S, C.; Marinelli, A.; Maxwell, T.; Motomura, K.; Mucke, M.; Natan, A.; Osipov, T.; Östlin, C.; Pernpointner, M.; Petrovic, V. S.; Robb, M. A.; Sathe, C.; Simpson, E. R.; Underwood, J. G.; Vacher, M.; Walke, D. J.; Wolf, T. J. A.; Zhaunerchyk, V.; Rubensson, J.-E.; Berrah, N.; Bucksbaum, P. H.; Ueda, K.; Feifel, R.; Frasinski, L. J.; Marangos, J. P.

    2015-12-01

    We report the first measurement of the near oxygen K-edge auger spectrum of the glycine molecule. Our work employed an x-ray free electron laser as the photon source operated with input photon energies tunable between 527 and 547 eV. Complete electron spectra were recorded at each photon energy in the tuning range, revealing resonant and non-resonant auger structures. Finally ab initio theoretical predictions are compared with the measured above the edge auger spectrum and an assignment of auger decay channels is performed.

  18. Sticking to (first) principles: quantum molecular dynamics and Bayesian probabilistic methods to simulate aquatic pollutant absorption spectra.

    PubMed

    Trerayapiwat, Kasidet; Ricke, Nathan; Cohen, Peter; Poblete, Alex; Rudel, Holly; Eustis, Soren N

    2016-08-10

    This work explores the relationship between theoretically predicted excitation energies and experimental molar absorption spectra as they pertain to environmental aquatic photochemistry. An overview of pertinent Quantum Chemical descriptions of sunlight-driven electronic transitions in organic pollutants is presented. Second, a combined molecular dynamics (MD), time-dependent density functional theory (TD-DFT) analysis of the ultraviolet to visible (UV-Vis) absorption spectra of six model organic compounds is presented alongside accurate experimental data. The functional relationship between the experimentally observed molar absorption spectrum and the discrete quantum transitions is examined. A rigorous comparison of the accuracy of the theoretical transition energies (ΔES0→Sn) and oscillator strength (fS0→Sn) is afforded by the probabilistic convolution and deconvolution procedure described. This method of deconvolution of experimental spectra using a Gaussian Mixture Model combined with Bayesian Information Criteria (BIC) to determine the mean (μ) and standard deviation (σ) as well as the number of observed singlet to singlet transition energy state distributions. This procedure allows a direct comparison of the one-electron (quantum) transitions that are the result of quantum chemical calculations and the ensemble of non-adiabatic quantum states that produce the macroscopic effect of a molar absorption spectrum. Poor agreement between the vertical excitation energies produced from TD-DFT calculations with five different functionals (CAM-B3LYP, PBE0, M06-2X, BP86, and LC-BLYP) suggest a failure of the theory to capture the low energy, environmentally important, electronic transitions in our model organic pollutants. However, the method of explicit-solvation of the organic solute using the quantum Effective Fragment Potential (EFP) in a density functional molecular dynamics trajectory simulation shows promise as a robust model of the hydrated organic

  19. High resolution infrared absorption spectra of various trace gases present in the upper atmosphere of the Earth

    NASA Technical Reports Server (NTRS)

    Hunt, Robert H.

    1988-01-01

    The objective of NASA Grant NsG 7473 was to obtain and analyze high resolution infrared absorption spectra of various trace gases present in the Earth's upper atmosphere. The goal of the spectral analysis was to obtain values of absorption line strengths, widths and frequencies of sufficient accuracy for use in upper atmosphere trace gas monitoring. During the early phase of the grant, high resolution spectra were obtained from two instruments. One was the 0.02/cm resolution vacuum grating spectrometer at the Florida State University and the other was the 0.01/cm resolution Fourier transform spectrometer at the McMath solar telescope at the Kitt Peak Observatory. Using these instruments, a considerable amount of spectra of methane and hydrogen peroxide were obtained and analyzed. During the latter years of the project, data taking was halted while efforts were devoted to building a new 0.0025/cm resolution vacuum Fourier transform spectrometer. Progress during this phase of the grant then became greatly slowed due to a lack of suitable graduate students in the program. However, the instrument was completed and brought to the point of producing interferograms.

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

    SciTech Connect

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

    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.

  1. [The absorption and fluorescence spectra of the cyanobacterial phycobilins of cryptoendolithic lichens in the high-polar region of Antarctica].

    PubMed

    Erokhina, L G; Shatilovich, A V; Kaminskaia, O P; Gilichinskiĭ, D A

    2002-01-01

    The algologically pure cultures of the green-brown cyanobacterium Chroococcidiopsis sp. and three cyanobacteria of the genus Gloeocapsa, the blue-green Gloeocapsa sp.1, the brown Gloeocapsa sp.2, and the red-orange Gloeocapsa sp.3, were isolated from sandstones and rock fissures in the high-polar regions of Antarctica. These cyanobacteria are the most widespread phycobionts of cryptoendolithic lichens in these regions. The comparative analysis of the absorption and the second-derivative absorption spectra of the cyanobacteria revealed considerable differences in the content of chlorophyll a and in the content and composition of carotenoids and phycobiliproteins. In addition to phycocyanin, allophycocyanin, and allophycocyanin B, which were present in all of the cyanobacteria studied, Gloeocapsa sp.2 also contained phycoerythrocyanin and Gloeocapsa sp.3 phycoerythrocyanin and C-phycoerythrin (the latter pigment is typical of nitrogen-fixing cyanobacteria). The fluorescence spectra of Gloeocapsa sp.2 and Gloeocapsa sp.3 considerably differed from the fluorescence spectra of the other cyanobacteria as well. The data obtained suggest that various zones of the lichens may be dominated either by photoheterotrophic or photoautotrophic cyanobacterial phycobionts, which differ in the content and composition of photosynthetic pigments.

  2. a Theoretical Model for Wide-Band Infrared-Absorption Molecular Spectra at any Pressure: Fiction or Reality?

    NASA Astrophysics Data System (ADS)

    Buldyreva, Jeanna; Vander Auwera, Jean

    2014-06-01

    Various atmospheric applications require modeling of infrared absorption by the main atmospheric species in wide ranges of frequencies, pressures and temperatures. For different pressure regimes, different mechanisms are responsible for the observed intensities of vibration-rotation line manifolds, and the structure of the bands changes drastically when going from low to high densities. Therefore, no universal theoretical model exists presently to interpret simultaneously collapsed band-shapes observed at very high pressures and isolated-line shapes recorded in sub-atmospheric regimes. Using CO_2 absorption spectra as an example, we introduce some improvements in the non-Markovian Energy-Corrected Sudden model, developed for high-density spectra of arbitrary tensorial rank and generalized recently to parallel and perpendicular infrared absorption bands, and test the applicability of this approach for the case of nearly Doppler pressure regime via comparisons with recently recorded experimental intensities. J.V. Buldyreva and L. Bonamy, Phys. Rev. A 60(1), 370-376 (1999). J. Buldyreva and L. Daneshvar, J. Chem. Phys. 139, 164107 (2013). L. Daneshvar, T. Földes, J. Buldyreva, J. Vander Auwera, J. Quant. Spectrosc. Radiat. Transfer 2014 (to be submitted).

  3. SYNCHROTRON POLARIZATION AND SYNCHROTRON SELF-ABSORPTION SPECTRA FOR A POWER-LAW PARTICLE DISTRIBUTION WITH FINITE ENERGY RANGE

    SciTech Connect

    Fouka, M.; Ouichaoui, S. E-mail: souichaoui@usthb.dz

    2011-12-10

    We have derived asymptotic forms for the degree of polarization of the optically thin synchrotron and for synchrotron self-absorption (SSA) spectra assuming a power-law particle distribution of the form N({gamma}) {approx} {gamma}{sup -p} with {gamma}{sub 1} < {gamma} < {gamma}{sub 2}, especially for a finite high-energy limit, {gamma}{sub 2}, in the case of an arbitrary pitch angle. The new results inferred concern more especially the high-frequency range x >> {eta}{sup 2} with parameter {eta} = {gamma}{sub 2}/{gamma}{sub 1}. The calculated SSA spectra concern instantaneous photon emission where cooling effects are not considered. They have been obtained by also ignoring likely effects such as Comptonization, pair creation and annihilation, as well as magnetic photon splitting. To that aim, in addition to the two usual absorption frequencies, a third possible one has been derived and expressed in terms of the Lambert W function based on the analytical asymptotic form of the absorption coefficient, {alpha}{sub {nu}}, for the high-frequency range {nu} >> {nu}{sub 2} (with {nu}{sub 2} the synchrotron frequency corresponding to {gamma}{sub 2}). We have shown that the latter frequency may not have realistic applications in astrophysics, except in the case of an adequate set of parameters allowing one to neglect Comptonization effects. More detailed calculations and discussions are presented.

  4. Synchrotron Polarization and Synchrotron Self-absorption Spectra for a Power-law Particle Distribution with Finite Energy Range

    NASA Astrophysics Data System (ADS)

    Fouka, M.; Ouichaoui, S.

    2011-12-01

    We have derived asymptotic forms for the degree of polarization of the optically thin synchrotron and for synchrotron self-absorption (SSA) spectra assuming a power-law particle distribution of the form N(γ) ~ γ-p with γ1 < γ < γ2, especially for a finite high-energy limit, γ2, in the case of an arbitrary pitch angle. The new results inferred concern more especially the high-frequency range x Gt η2 with parameter η = γ2/γ1. The calculated SSA spectra concern instantaneous photon emission where cooling effects are not considered. They have been obtained by also ignoring likely effects such as Comptonization, pair creation and annihilation, as well as magnetic photon splitting. To that aim, in addition to the two usual absorption frequencies, a third possible one has been derived and expressed in terms of the Lambert W function based on the analytical asymptotic form of the absorption coefficient, αν, for the high-frequency range ν Gt ν2 (with ν2 the synchrotron frequency corresponding to γ2). We have shown that the latter frequency may not have realistic applications in astrophysics, except in the case of an adequate set of parameters allowing one to neglect Comptonization effects. More detailed calculations and discussions are presented.

  5. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm

    NASA Astrophysics Data System (ADS)

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-01

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  6. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Liu, Zhongfang; Liu, Jiangtao; Liu, Shaopu; Shen, Wei

    2008-03-01

    In pH 4.4-4.5 Britton-Robinson (BR) buffer solution, fluoroquinolone antibiotics (FLQs) including ciprofloxacin (CIP), norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) could react with erythrosine (Ery) to form 1:1 ion-association complexes, which not only resulted in the changes of the absorption spectra and the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS). These offered some indications of the determination of fluoroquinolone antibiotics by spectrophotometric, fluorescence and resonance Rayleigh scattering methods. The detection limits for fluoroquinolone antibiotics were in the range of 0.097-0.265 μg/mL for absorption methods, 0.022-0.100 μg/mL for fluorophotometry and 0.014-0.027 μg/mL for RRS method, respectively. Among them, the RRS method had the highest sensitivity. In this work, the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions and the properties of the analytical chemistry were investigated. The methods have been successfully applied to determination of some fluoroquinolone antibiotics in human urine samples and tablets. Taking CIP-Ery system as an example, the charge distribution, the enthalpy of formation and the mean polarizability were calculated by density function theory (DFT) method. In addition, the reasons for the enhancement of scattering spectra were discussed.

  7. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm.

    PubMed

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-28

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  8. Electronic transitions and fermi edge singularity in polar heterostructures studied by absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Pandey, S.; Cavalcoli, D.; Minj, A.; Fraboni, B.; Cavallini, A.; Gamarra, P.; Poisson, M. A.

    2012-12-01

    Optically induced electronic transitions in nitride based polar heterostructures have been investigated by absorption and emission spectroscopy. Surface photovoltage (SPV), photocurrent (PC), and photo luminescence spectroscopy have been applied to high quality InAlN/AlN/GaN structures to study the optical properties of two dimensional electron gas. Energy levels within the two dimensional electron gas (2DEG) well at the interface between the GaN and AlN have been directly observed by SPV and PC. Moreover, a strong enhancement of the photoluminescence intensity due to holes recombining with electrons at the Fermi Energy, known as fermi energy singularity, has been observed. These analyses have been carried out on InAlN/AlN/GaN heterojunctions with the InAlN barrier layer having different In content, a parameter which affects the energy levels within the 2DEG well as well as the optical signal intensity. The measured energy values are in a very good agreement with the ones obtained by Schrödinger-Poisson simulations.

  9. Studying the complex absorption profiles of Si IV in 21 HiBALQSO spectra

    NASA Astrophysics Data System (ADS)

    Stathopoulos, D.; Danezis, E.; Lyratzi, E.; Antoniou, A.; Popović, L. Č.; Tzimeas, D.; Dimitrijević, M. S.

    2014-12-01

    We investigate the physical conditions and kinematics of broad absorption line region clouds of Si IV in 21 HiBAL Quasars. We use the Danezis et al. method [1], [2], [3] in order to fit and analyze the broad absorption troughs of Si IV resonance lines in the UV region of the electromagnetic spectrum. We find that the BAL flow is not smooth but instead plasma clouds are formed in it. BAL troughs present multicomponent structure which indicates the existence of more than one absorbing cloud in the line of sight, where every absorbing cloud produces a Si IV doublet. We show that the blending of these doublets produces the apparent broad absorption troughs we observe. One of our main achievements is that we managed to decompose and deblend each complex absorption trough to the individual doublets that it consists of. Apart from that, we succeeded in deblending the resonance lines of every doublet. By achieving accurate fits to the BAL troughs we calculated some physical and kinematical parameters that describe the plasma clouds in the line of sight. These parameters are: the radial outflow velocities of the clouds, the random velocities of ions inside each plasma cloud, the apparent optical depth in the center of every absorption component, the FWHM and the equivalent width. As a final step we correlate these physical parameters in order to draw useful conclusions.

  10. Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection–Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies

    PubMed Central

    2014-01-01

    Atomistic level understanding of interaction of α,β-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C=C or C=O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on α,β-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflection–absorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments, and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C=C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated π system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both π bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated π system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111). PMID:26089998

  11. Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies.

    PubMed

    Dostert, Karl-Heinz; O'Brien, Casey P; Riedel, Wiebke; Savara, Aditya; Liu, Wei; Oehzelt, Martin; Tkatchenko, Alexandre; Schauermann, Swetlana

    2014-12-04

    Atomistic level understanding of interaction of α,β-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C=C or C=O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on α,β-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflection-absorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments, and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C=C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated π system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both π bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated π system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111).

  12. The UV absorption of nucleobases: semi-classical ab initio spectra simulations.

    PubMed

    Barbatti, Mario; Aquino, Adelia J A; Lischka, Hans

    2010-05-21

    Semi-classical simulations of the UV-photoabsorption cross sections of adenine, guanine, cytosine, thymine, and uracil in gas phase were performed at the resolution-of-identity coupled cluster to the second-order (RI-CC2) level. With the exception of cytosine, the spectra of the other four nucleobases show a two band pattern separated by a low intensity region. The spectrum of cytosine is shaped by a sequence of three bands of increasing intensity. The first band of guanine is composed by two pipi* transitions of similar intensities. The analysis of individual contributions to the spectra allows a detailed assignment of bands. It is shown that the semi-classical simulations are able to predict general features of the experimental spectra, including their absolute intensities.

  13. Optical absorption spectra and structures of Ag{6/+} and Ag{8/+}

    NASA Astrophysics Data System (ADS)

    Shayeghi, A.; Götz, D. A.; Johnston, R. L.; Schäfer, R.

    2015-06-01

    This work presents optical photodissociation spectra of the Ag{6/+} and the Ag{8/+} clusters in the photon energy range ħω = 1.9-4.4 eV. Experimental spectra are interpreted by means of range separated TDDFT using the LC- ωPBEh and HSE06 functionals, where putative global minimum structures are obtained by the new pool-based Birmingham Cluster Genetic Algorithm, coupled with density functional theory. Structural assignment is facilitated by additionally taking data from previous ion mobility experiments into account. Both functionals reproduce the measured spectra very well, whereas HSE06 shows an almost quantitative agreement, questioning the importance of Hartree-Fock exchange in the long-range part of the range separated functional.

  14. On the time-dependent calculation of angular averaged vibronic absorption spectra with an application to molecular aggregates

    NASA Astrophysics Data System (ADS)

    Brüning, Christoph; Engel, Volker

    2017-01-01

    We introduce an efficient method to determine angular averaged absorption spectra for cases where electronic transitions take place to a manifold of N coupled excited states. The approach rests on the calculation of time-dependent auto-correlation functions which, upon Fourier-transform yield the spectrum. Assuming the Condon-approximation, it is shown that three wave-packet propagations are sufficient to calculate the spectrum. This is in contrast to a direct approach where it is necessary to perform N propagations to arrive at N2 cross-correlation functions. The reduction in computation time is of importance for larger molecular aggregates where the number N is determined by the aggregate size. We provide an example by determining spectra for macrocyclic dyes in different dipole-geometries.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. All-electron first-principles GW+Bethe-Salpeter calculation for optical absorption spectra of sodium clusters

    SciTech Connect

    Noguchi, Yoshifumi; Ohno, Kaoru

    2010-04-15

    The optical absorption spectra of sodium clusters (Na{sub 2n}, n{<=} 4) are calculated by using an all-electron first-principles GW+Bethe-Salpeter method with the mixed-basis approach within the Tamm-Dancoff approximation. In these small systems, the excitonic effect strongly affects the optical properties due to the confinement of exciton in the small system size. The present state-of-the-art method treats the electron-hole two-particle Green's function by incorporating the ladder diagrams up to the infinite order and therefore takes into account the excitonic effect in a good approximation. We check the accuracy of the present method by comparing the resulting spectra with experiments. In addition, the effect of delocalization in particular in the lowest unoccupied molecular orbital in the GW quasiparticle wave function is also discussed by rediagonalizing the Dyson equation.

  17. The effect of absorption and coherent interference in the photoluminescence and electroluminescence spectra of SRO/SRN MIS capacitors.

    PubMed

    Juvert, Joan; González-Fernández, Alfredo Abelardo; Llobera, Andreu; Domínguez, Carlos

    2013-04-22

    In this paper we present a technique that can be used to study the effect of absorption and coherent interference in the luminescence of multilayer structures. We apply the technique to the measured photoluminescence and electroluminescence spectra of MIS capacitors where the insulator is composed of a silicon rich oxide (SRO)/silicon rich nitride (SRN) bilayer structure. We remove the effect of the multilayer stack on the measured photoluminescence spectrum of the samples without the metal contact to find the intrinsic spectrum. Then we apply the effect of the MIS structure on the intrinsic spectrum in order to calculate the electroluminescence spectrum. Good agreement with the experimentally measured EL spectrum is found. We discuss which parameters affect the spectra most significantly.

  18. Cooperative enhancement of TPA in cruciform double-chain DSB derivation: a femtosecond transient absorption spectra study

    NASA Astrophysics Data System (ADS)

    He, X.; Wang, Y.; Yang, Z.; Ma, Y.; Yang, Y.

    2010-09-01

    Femtosecond time-resolved transient absorption (TA) spectra study was adopted to study the mechanism of the cooperative enhancement of two-photon absorption (TPA) cross section from the linear structure 1,4-di(4'-N,N-diphenylaminostyryl)benzene (DPA-DSB) to its cruciform double-chain dimer DPA-TSB. The results suggested that a non-emissive intramolecular charge-transfer (ICT) state, ICT’, was present upon excitation in the dimer, which was absent in the monomer. The existence of this non-emissive state, indicating the enhancement of the intramolecular charge-transfer of the dimer, should be the reason for the cooperative enhancement of the TPA cross section of the dimer compared to the monomer.

  19. First detection of ionized helium absorption lines in infrared K band spectra of O-type stars

    NASA Technical Reports Server (NTRS)

    Conti, Peter S.; Block, David L.; Geballe, T. R.; Hanson, Margaret M.

    1993-01-01

    We have obtained high SNR, moderate-resolution K band spectra of two early O-type main sequence stars, HD 46150 O5 V, and HD 46223 O4 V, in the Rosette Nebula. We report the detection, for the first time, of the 2.189 micron He II line in O-type stars. Also detected is the 2.1661 micron Br-gamma line in absorption. The 2.058 micron He I line appears to be present in absorption in both stars, although its appearance at our resolution is complicated by atmospheric features. These three lines can form the basis for a spectral classification system for hot stars in the K band that may be used at infrared wavelengths to elucidate the nature of those luminous stars in otherwise obscured H II and giant H II regions.

  20. Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction

    PubMed Central

    2015-01-01

    We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Δm is mainly caused by dispersion effects and depends sensitively on the molecule’s specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Δm= −QWm in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while Wm is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI). PMID:25834658