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Sample records for absorption band edge

  1. 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.

  2. 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.

  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. Sub-gap and band edge optical absorption in a-Si:H by photothermal deflection spectroscopy

    NASA Astrophysics Data System (ADS)

    Jackson, W. B.; Amer, N. M.

    1981-07-01

    Using photothermal deflection spectroscopy, the optical absorption of various a-Si:H films was investigated in the range of 2.1 to 0.6 eV. An absorption shoulder which depends on deposition conditions and on doping was found and was attributed to dangling bonds. The exponential edge broadens with increasing spin density.

  5. X-ray absorption and reflection as probes of the GaN conduction bands: Theory and experiment of the N K-edge and Ga M{sub 2,3} edges

    SciTech Connect

    Lambrecht, W.R.L.; Rashkeev, S.N.; Segall, B.; Lawniczak-Jablonska, K.; Suski, T.; Gullikson, E.M.; Underwood, J.H.; Perera, R.C.C.; Rife, J.C.

    1997-12-31

    X-ray absorption and glancing angle reflectivity measurements in the energy range of the Nitrogen K-edge and Gallium M{sub 2,3} edges are reported. Linear muffin-tin orbital band-structure and spectral function calculations are used to interpret the data. Polarization effects are evidenced for the N-K-edge spectra by comparing X-ray reflectivity in s- and p-polarized light.

  6. Band-Selective Measurements of Electron Dynamics in VO2 UsingFemtosecond Near-Edge X-Ray Absorption

    SciTech Connect

    Cavalleri, A.; Rini, M.; Chong, H.H.W.; Fourmaux, S.; Glover,T.E.; Heimann, P.A.; Kieffer, J.C.; Schoenlein, R.W.

    2005-07-20

    We report on the first demonstration of femtosecond x-rayabsorption spectroscopy, made uniquely possible by the use of broadlytunable bending-magnet radiation from "laser-sliced" electron buncheswithin a synchrotron storage ri ng. We measure the femtosecond electronicrearrangements that occur during the photoinduced insulator-metal phasetransition in VO2. Symmetry- and element-specific x-ray absorption fromV2p and O1s core levels (near 500 eV) separately measures the fillingdynamics of differently hybridized V3d-O2p electronic bands near theFermi level.

  7. Flat-band engineering of mobility edges

    NASA Astrophysics Data System (ADS)

    Danieli, Carlo; Bodyfelt, Joshua D.; Flach, Sergej

    2015-06-01

    Properly modulated flat-band lattices have a divergent density of states at the flat-band energy. Quasiperiodic modulations are known to host a metal-insulator transition already in one space dimension. Their embedding into flat-band geometries consequently allows for a precise engineering and fine tuning of mobility edges. We obtain analytic expressions for singular mobility edges for two flat-band lattice examples. In particular, we engineer cases with arbitrarily small energy separations of mobility edge, zeroes, and divergencies.

  8. The Red Edge Problem in asteroid band parameter analysis

    NASA Astrophysics Data System (ADS)

    Lindsay, Sean S.; Dunn, Tasha L.; Emery, Joshua P.; Bowles, Neil E.

    2016-04-01

    Near-infrared reflectance spectra of S-type asteroids contain two absorptions at 1 and 2 μm (band I and II) that are diagnostic of mineralogy. A parameterization of these two bands is frequently employed to determine the mineralogy of S(IV) asteroids through the use of ordinary chondrite calibration equations that link the mineralogy to band parameters. The most widely used calibration study uses a Band II terminal wavelength point (red edge) at 2.50 μm. However, due to the limitations of the NIR detectors on prominent telescopes used in asteroid research, spectral data for asteroids are typically only reliable out to 2.45 μm. We refer to this discrepancy as "The Red Edge Problem." In this report, we evaluate the associated errors for measured band area ratios (BAR = Area BII/BI) and calculated relative abundance measurements. We find that the Red Edge Problem is often not the dominant source of error for the observationally limited red edge set at 2.45 μm, but it frequently is for a red edge set at 2.40 μm. The error, however, is one sided and therefore systematic. As such, we provide equations to adjust measured BARs to values with a different red edge definition. We also provide new ol/(ol+px) calibration equations for red edges set at 2.40 and 2.45 μm.

  9. The electronic absorption edge of petroleum

    SciTech Connect

    Mullins, O.C.; Mitra-Kirtley, S.; Zhu, Yifu

    1992-09-01

    The electronic absorption spectra of more than 20 crude oils and asphaltenes are examined. The spectral location of the electronic absorption edge varies over a wide range, from the near-infrared for heavy oils and asphaltenes to the near-UV for gas condensates. The functional form of the electronic absorption edge for all crude oils (measured) is characteristic of the {open_quotes}Urbach tail,{close_quotes} a phenomenology which describes electronic absorption edges in wide-ranging materials. The crude oils all show similar Urbach widths, which are significantly larger than those generally found for various materials but are similar to those previously reported for asphaltenes. Monotonically increasing absorption at higher photon energy continues for all crude oils until the spectral region is reached where single-ring aromatics dominate absorption. However, the rate of increasing absorption at higher energies moderates, thereby deviating from the Urbach behavior. Fluorescence emission spectra exhibit small red shifts from the excitation wavelength and small fluorescence peak widths in the Urbach regions of different crude oils, but show large red shifts and large peak widths in spectral regions which deviate from the Urbach behavior. This observation implies that the Urbach spectral region is dominated by lowest-energy electronic absorption of corresponding chromophores. Thus, the Urbach tail gives a direct measure of the population distribution of chromophores in crude oils. Implied population distributions are consistent with thermally activated growth of large chromophores from small ones. 12 refs., 8 figs.

  10. 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.

  11. Search for Lyman Limit Absorption Edge in Quasar Continuum

    NASA Astrophysics Data System (ADS)

    Sun, W.-H.; Malkan, M. A.; Chang, Thomas H. W.

    1993-12-01

    We examine the low resolution UV spectra of the 37 quasars in HST Key Project to search for intrinsic Lyman absorption edge which may be a signature of thermal accretion disks. Only 28 QSOs have proper redshifts to place the region of interest in the G160L window. We fit the L_β with two gaussians to remove the line. We then avoid 20 and 50 Angstroms on the blue and red sides of 912 Angstroms in the rest frame, and take 80 Angstroms bins (rest frame) on both sides but further out for analysis. We compare the single power-law fitting (to the entire range across the edge), with the two power-law fitting to blue and red bands. We also measure the percentage drop of flux over the Lyman limit. There are 7 objects with intrinsically noisy spectra, which were presumably caused by intervening Lyman absorption systems. Applying the two methods on the rest 21 objects, we found {24%} candidates to have possible rest frame Lyman limit absorption edges. Same analyses have also been performed on optical spectra of medium- to high-redshift QSOs from Lick Observatory and Hale Observatory. Similar results were also found.

  12. Atmospheric Solar Heating in Minor Absorption Bands

    NASA Technical Reports Server (NTRS)

    Chou, Ming-Dah

    1998-01-01

    Solar radiation is the primary source of energy driving atmospheric and oceanic circulations. Concerned with the huge computing time required for computing radiative transfer in weather and climate models, solar heating in minor absorption bands has often been neglected. The individual contributions of these minor bands to the atmospheric heating is small, but collectively they are not negligible. The solar heating in minor bands includes the absorption due to water vapor in the photosynthetically active radiation (PAR) spectral region from 14284/cm to 25000/cm, the ozone absorption and Rayleigh scattering in the near infrared, as well as the O2 and CO2 absorption in a number of weak bands. Detailed high spectral- and angular-resolution calculations show that the total effect of these minor absorption is to enhance the atmospheric solar heating by approximately 10%. Depending upon the strength of the absorption and the overlapping among gaseous absorption, different approaches are applied to parameterize these minor absorption. The parameterizations are accurate and require little extra time for computing radiative fluxes. They have been efficiently implemented in the various atmospheric models at NASA/Goddard Space Flight Center, including cloud ensemble, mesoscale, and climate models.

  13. Near band edge anisotropic optical transitions in wide band gap semiconductor Cu2ZnSiS4

    NASA Astrophysics Data System (ADS)

    Levcenco, S.; Dumcenco, D.; Huang, Y. S.; Arushanov, E.; Tezlevan, V.; Tiong, K. K.; Du, C. H.

    2010-10-01

    In this study, anisotropic near band edge transitions of Cu2ZnSiS4 single crystals grown by chemical vapor transport were characterized by using polarization-dependent absorption, piezoreflectance (PzR) and surface photovoltage (SPV) spectroscopy techniques at room temperature. The measurements were carried out on the as grown basal plane with the normal along [2 1 0] and the axis c parallel to the long edge of the crystal platelet. Analysis of absorption and SPV spectra reveal indirect allowed transitions for the absorption edge of Cu2ZnSiS4. The estimated values of indirect band gap are 2.97 eV and 3.07 eV, respectively, for E ⊥c and E ∥c polarization configurations. The polarization-dependent PzR and SPV spectra in the vicinity of the direct band gap of Cu2ZnSiS4 reveal features E⊥ex and E∥ex at around 3.32 eV and 3.41 eV for E ⊥c and E ∥c polarizations, respectively. Both features E⊥ex and E∥ex are associated with the interband excitonic transitions at point Γ and can be explained by crystal-field splitting of valence band. Based on the experimental observations, a plausible band structure near band edge of Cu2ZnSiS4 is proposed.

  14. New Kronig-Penney Equation Emphasizing the Band Edge Conditions

    ERIC Educational Resources Information Center

    Szmulowicz, Frank

    2008-01-01

    The Kronig-Penney problem is a textbook example for discussing band dispersions and band gap formation in periodic layered media. For example, in photonic crystals, the behaviour of bands next to the band edges is important for further discussions of such effects as inhibited light emission, slow light and negative index of refraction. However,…

  15. Optically decomposed near-band-edge structure and excitonic transitions in Ga2S3

    PubMed Central

    Ho, Ching-Hwa; Chen, Hsin-Hung

    2014-01-01

    The band-edge structure and band gap are key parameters for a functional chalcogenide semiconductor to its applications in optoelectronics, nanoelectronics, and photonics devices. Here, we firstly demonstrate the complete study of experimental band-edge structure and excitonic transitions of monoclinic digallium trisulfide (Ga2S3) using photoluminescence (PL), thermoreflectance (TR), and optical absorption measurements at low and room temperatures. According to the experimental results of optical measurements, three band-edge transitions of EA = 3.052 eV, EB = 3.240 eV, and EC = 3.328 eV are respectively determined and they are proven to construct the main band-edge structure of Ga2S3. Distinctly optical-anisotropic behaviors by orientation- and polarization-dependent TR measurements are, respectively, relevant to distinguish the origins of the EA, EB, and EC transitions. The results indicated that the three band-edge transitions are coming from different origins. Low-temperature PL results show defect emissions, bound-exciton and free-exciton luminescences in the radiation spectra of Ga2S3. The below-band-edge transitions are respectively characterized. On the basis of experimental analyses, the optical property of near-band-edge structure and excitonic transitions in the monoclinic Ga2S3 crystal is revealed. PMID:25142550

  16. Tungsten band edge absorber/emitter based on a monolayer of ceramic microspheres.

    PubMed

    Dyachenko, P N; do Rosário, J J; Leib, E W; Petrov, A Yu; Störmer, M; Weller, H; Vossmeyer, T; Schneider, G A; Eich, M

    2015-09-21

    We report on a band edge absorber/emitter design for high-temperature applications based on an unstructured tungsten substrate and a monolayer of ceramic microspheres. The absorber was fabricated as a monolayer of ZrO(2) microparticles on a tungsten layer with a HfO(2) nanocoating. The band edge of the absorption is based on critically coupled microsphere resonances. It can be tuned from visible to near-infrared range by varying the diameter of the microparticles. The absorption properties were found to be stable up to 1000°C. PMID:26406752

  17. Highly dispersive photonic band-gap-edge optofluidic biosensors

    NASA Astrophysics Data System (ADS)

    Xiao, S.; Mortensen, N. A.

    2006-11-01

    Highly dispersive photonic band-gap-edge optofluidic biosensors are studied theoretically. We demonstrate that these structures are strongly sensitive to the refractive index of the liquid, which is used to tune dispersion of the photonic crystal. The upper frequency band-gap edge shifts about 1.8 nm for δ n=0.002, which is quite sensitive. Results from transmission spectra agree well with those obtained from the band structure theory.

  18. Temperature dependence of the absorption edge of vitreous silica

    NASA Technical Reports Server (NTRS)

    Bates, C. W., Jr.

    1976-01-01

    During an investigation of the optical properties of high-purity vitreous silica (fused quartz), which is being developed by NASA as a reflective and ablative heat shield, some interesting properties of theoretical and experimental nature have become apparent which otherwise may have remained unnoticed. Of particular interest for the NASA application is the shift of the absorption edge toward longer wavelengths with increasing temperature. The results of studies of this shift and of the spectral dependence of the absorption edge are summarized in the present paper. Plots of the absorption edge and the absorption spectrum of fused quartz vs temperature are given and discussed.

  19. Degenerate band edge resonances in periodic silicon ridge waveguides.

    PubMed

    Wood, Michael G; Burr, Justin R; Reano, Ronald M

    2015-06-01

    We experimentally demonstrate degenerate band edge resonances in periodic Si ridge waveguides that are compatible with carrier injection modulation for active electro-optical devices. The resonant cavities are designed using a combination of the plane-wave expansion method and the finite difference time domain technique. Measured and simulated quality factors of the first band edge resonances scale to the fifth power of the number of periods. Quality factor scaling is determined to be limited by fabrication imperfections. Compared to resonators based on a regular transmission band edge, degenerate band edge devices can achieve significantly larger quality factors in the same number of periods. Applications include compact electro-optical switches, modulators, and sensors that benefit from high-quality factors and large distributed electric fields. PMID:26030540

  20. Absorption band Q model for the Earth

    NASA Technical Reports Server (NTRS)

    Anderson, D. L.; Given, J. W.

    1981-01-01

    Attenuation in solids and liquids, as measured by the quality factor Q, is typically frequency dependent. In seismology, however, Q is usually assumed to be independent of frequency. Body wave, surface wave, and normal mode data are used to place constraints on the frequency dependence of Q in the mantle. Specific features of the absorption band model are: low-Q in the seismic band at both the top and the base of the mantle, low-Q for long-period body waves in the outer core, an inner core Q sub s that increases with period, and low Q sub p/Q sub s at short periods in the middle mantle.

  1. 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}.

  2. Absorption-edge calculations of inorganic nonlinear optical crystals

    NASA Astrophysics Data System (ADS)

    Wu, Kechen; Chen, Chuangtian

    1992-03-01

    A theoretical model suitable for calculating absorption edges of inorganic nonlinear optical (NLO) crystals is introduced. This model is proved to be useful to elucidate the relationship between electronic structures of NLO-active groups and macroscopic properties of absorption edges on the UV side of most of the inorganic nonlinear optical crystals. A systematic calculation of absorption edges on the UV side for several important inorganic NLO crystals is carried out by means of DV-SCM-Xα method and all calculated results are in good agreement with experimental data. These inorganic NLO crystals include LiB3O5(LBO), β-BaB2O4(BBO), KB5, KDP, Na2SbF5, Ba2TiSi2O8, iodate and NaNO2. The calculated energy level structures of LiB3O5 and β-BaB2O4 crystals are compared with the measured XPS spectra. The unusual transparent spectra of KB5 and KDP crystals are partly explained from the microstructure point of view. The effect of lone electron pair in iodate and NaNO2 crystals on their absorption edges are discussed. All these results show that Anionic Group Theory of Nonlinear Optical Crystals is useful to evaluate the absorption edges of the inorganic nonlinear optical crystal and is a powerful tool in a Molecular Engineering approach to search for new nonlinear optical materials.

  3. 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.

  4. Measurement of the depolarization ratio of Rayleigh scattering at absorption bands

    NASA Astrophysics Data System (ADS)

    Anglister, J.; Steinberg, I. Z.

    1981-01-01

    Measurements of the depolarization ratio ρv of light scattered by the pigments lycopene and β-carotene at the red part of their absorption bands yielded values which are very close to the theoretical value 1/3 of a fully anisotropic molecular polarizability, i.e., that due to an electric dipole moment. Measurements of ρv at the blue edge of the visible absorption band of pinacyanol chloride yielded a value of 0.75 at 472.2 nm, which is the maximum value that a depolarization ratio can assume, and is attained if the average molecular polarizability is zero. This is possible only if the diagonalized polarizability tensor has at least one negative element to counterbalance the positive ones. A negative refractive index at the blue edge of the absorption band is thus experimentally demonstrated.

  5. Impurity Sub-Band in Heavily Cu-Doped InAs Nanocrystal Quantum Dots Detected by Ultrafast Transient Absorption.

    PubMed

    Yang, Chunfan; Faust, Adam; Amit, Yorai; Gdor, Itay; Banin, Uri; Ruhman, Sanford

    2016-05-19

    The effect of Cu impurities on the absorption cross section, the rate of hot exction thermalization, and on exciton recombination processes in InAs quantum dots was studied by femtosecond transient absorption. Our findings reveal dynamic spectral effects of an emergent impurity sub-band near the bottom of the conduction band. Previously hypothesized to explain static photophysical properties of this system, its presence is shown to shorten hot carrier relaxation. Partial redistribution of interband oscillator strength to sub-band levels reduces the band edge bleach per exciton progressively with the degree of doping, even though the total linear absorption cross section at the band edge remains unchanged. In contrast, no doping effects were detected on absorption cross sections high in the conduction band, as expected due to the relatively high density of sates of the undoped QDs. PMID:26720008

  6. Defects forming the optical absorption edge in TlGaSe2 layered crystal

    NASA Astrophysics Data System (ADS)

    Seyidov, MirHasan Yu.; Suleymanov, Rauf A.; Şale, Yasin

    2016-09-01

    In this work, we present the results of optical experiments designed to investigate the changes in optical absorption spectra of TlGaSe2 ferroelectric-semiconductor with incommensurate (INC) phase in experimental conditions where crystal is kept several hours within the INC-phase (the regime of so called "memory" effect). The fundamental absorption of TlGaSe2, experimentally investigated by optical transmission measurements performed in the temperature range 15-300 K. An extraordinary modification of the optical absorption edge in the range of Urbach's tail is discovered as a result of the annealing within the INC-phase. The role of native defects forming the band edge in the observed phenomena in TlGaSe2 is discussed.

  7. X-ray absorption near edge structure investigation ofvanadium-doped ZnO thin films

    SciTech Connect

    Faiz, M.; Tabet, N.; Mekki, A.; Mun, B.S.; Hussain, Z.

    2006-05-11

    X-ray absorption near edge structure spectroscopy has beenused to investigate the electronic and atomic structure of vanadium-dopedZnO thin films obtained by reactive plasma. The results show no sign ofmetallic clustering of V atoms, +4 oxidation state of V, 4-foldcoordination of Zn in the films, and a secondary phase (possibly VO2)formation at 15 percent V doping. O K edge spectra show V 3d-O 2p and Zn4d-O 2p hybridization, and suggest that V4+ acts as electron donor thatfills the sigma* band.

  8. Validity of the concept of band edge in organic semiconductors

    NASA Astrophysics Data System (ADS)

    Horowitz, Gilles

    2015-09-01

    Because most organic semiconductors are disordered, the more appropriate function to describe their density of states (DOS) is the Gaussian distribution. A striking difference between the Gaussian DOS and the parabolic DOS found in conventional inorganic semiconductors is the fact that it does not allow for a simple and straightforward definition of the band edge. The most usual way found in the literature to define the band edge of a Gaussian DOS consists of extrapolating the tangent to the inflection point of the Gaussian curve. The aim of this paper is to discuss the validity of such a way of conduct. An analysis of data found in the literature shows that the width of the Gaussian distribution is significantly larger than what usually retained in transport models. It is also shown that the validity of the usual definition for the band edge is questioned by the fact that the density of charge carriers behave as a degenerate distribution, even at relatively low doping levels.

  9. Band-Gap and Band-Edge Engineering of Multicomponent Garnet Scintillators from First Principles

    NASA Astrophysics Data System (ADS)

    Yadav, Satyesh K.; Uberuaga, Blas P.; Nikl, Martin; Jiang, Chao; Stanek, Christopher R.

    2015-11-01

    Complex doping schemes in R3 Al5 O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-band maximum (VBM). We consider two sets of compositions based on Lu3 B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5 O12 , where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. This approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  11. Light harvesting in photonic crystals revisited: why do slow photons at the blue edge enhance absorption?

    PubMed

    Deparis, O; Mouchet, S R; Su, B-L

    2015-11-11

    Light harvesting enhancement by slow photons in photonic crystal catalysts or dye-sensitized solar cells is a promising approach for increasing the efficiency of photoreactions. This structural effect is exploited in inverse opal TiO2 photocatalysts by tuning the red edge of the photonic band gap to the TiO2 electronic excitation band edge. In spite of many experimental demonstrations, the slow photon effect is not fully understood yet. In particular, observed enhancement by tuning the blue edge has remained unexplained. Based on rigorous couple wave analysis simulations, we quantify light harvesting enhancement in terms of absorption increase at a specific wavelength (monochromatic UV illumination) or photocurrent increase (solar light illumination), with respect to homogeneous flat slab of equivalent material thickness. We show that the commonly accepted explanation relying on light intensity confinement in high (low) dielectric constant regions at the red (blue) edge is challenged in the case of TiO2 inverse opals because of the sub-wavelength size of the material skeleton. The reason why slow photons at the blue edge are also able to enhance light harvesting is the loose confinement of the field, which leads to significant resonantly enhanced field intensity overlap with the skeleton in both red and blue edge tuning cases, yet with different intensity patterns. PMID:26517229

  12. Band-gap and band-edge engineering of multicomponent garnet scintillators from first principles

    DOE PAGESBeta

    Yadav, Satyesh K.; Uberuaga, Blas P.; Nikl, Martin; Jiang, Chao; Stanek, Christopher R.

    2015-11-24

    Complex doping schemes in R3Al5O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-bandmore » maximum (VBM). We consider two sets of compositions based on Lu3B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5O12, where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. Furthermore, this approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.« less

  13. Soft X-ray Absorption Edges in LMXBs

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The XMM observation of LMC X-2 is part of our program to study X-ray absorption in the interstellar medium (ISM). This program includes a variety of bright X-ray binaries in the Galaxy as well as the Magellanic Clouds (LMC and SMC). LMC X-2 is located near the heart of the LMC. Its very soft X-ray spectrum is used to determine abundance and ionization fractions of neutral and lowly ionized oxygen of the ISM in the LMC. The RGS spectrum so far allowed us to determine the O-edge value to be for atomic O, the EW of O-I in the ls-2p resonance absorption line, and the same for O-II. The current study is still ongoing in conjunction with other low absorption sources like Sco X-1 and the recently observed X-ray binary 4U 1957+11.

  14. Investigation of band gap narrowing in nitrogen-doped La2Ti2O7 with transient absorption spectroscopy.

    PubMed

    Yost, Brandon T; Cushing, Scott K; Meng, Fanke; Bright, Joeseph; Bas, Derek A; Wu, Nianqiang; Bristow, Alan D

    2015-12-14

    Doping a semiconductor can extend the light absorption range, however, it usually introduces mid-gap states, reducing the charge carrier lifetime. This report shows that doping lanthanum dititinate (La2Ti2O7) with nitrogen extends the valence band edge by creating a continuum of dopant states, increasing the light absorption edge from 380 nm to 550 nm without adding mid-gap states. The dopant states are experimentally resolved in the excited state by correlating transient absorption spectroscopy with a supercontinuum probe and DFT prediction. The lack of mid-gap states is further confirmed by measuring the excited state lifetimes, which reveal the shifted band edge only increased carrier thermalization rates to the band edge and not interband charge recombination under both ultraviolet and visible excitation. Terahertz (time-domain) spectroscopy also reveals that the conduction mechanism remains unchanged after doping, suggesting the states are delocalized. PMID:26531849

  15. Band-gap and band-edge engineering of multicomponent garnet scintillators from first principles

    SciTech Connect

    Yadav, Satyesh K.; Uberuaga, Blas P.; Nikl, Martin; Jiang, Chao; Stanek, Christopher R.

    2015-11-24

    Complex doping schemes in R3Al5O12 (where R is the rare-earth element) garnet compounds have recently led to pronounced improvements in scintillator performance. Specifically, by admixing lutetium and yttrium aluminate garnets with gallium and gadolinium, the band gap is altered in a manner that facilitates the removal of deleterious electron trapping associated with cation antisite defects. Here, we expand upon this initial work to systematically investigate the effect of substitutional admixing on the energy levels of band edges. Density-functional theory and hybrid density-functional theory (HDFT) are used to survey potential admixing candidates that modify either the conduction-band minimum (CBM) or valence-band maximum (VBM). We consider two sets of compositions based on Lu3B5O12 where B is Al, Ga, In, As, and Sb, and R3Al5O12, where R is Lu, Gd, Dy, and Er. We find that admixing with various R cations does not appreciably affect the band gap or band edges. In contrast, substituting Al with cations of dissimilar ionic radii has a profound impact on the band structure. We further show that certain dopants can be used to selectively modify only the CBM or the VBM. Specifically, Ga and In decrease the band gap by lowering the CBM, while As and Sb decrease the band gap by raising the VBM, the relative change in band gap is quantitatively validated by HDFT. These results demonstrate a powerful approach to quickly screen the impact of dopants on the electronic structure of scintillator compounds, identifying those dopants which alter the band edges in very specific ways to eliminate both electron and hole traps responsible for performance limitations. Furthermore, this approach should be broadly applicable for the optimization of electronic and optical performance for a wide range of compounds by tuning the VBM and CBM.

  16. Tuning semiconductor band edge energies for solar photocatalysis via surface ligand passivation.

    PubMed

    Yang, Shenyuan; Prendergast, David; Neaton, Jeffrey B

    2012-01-11

    Semiconductor photocatalysts capable of broadband solar photon absorption may be nonetheless precluded from use in driving water splitting and other solar-to-fuel related reactions due to unfavorable band edge energy alignment. Using first-principles density functional theory and beyond, we calculate the electronic structure of passivated CdSe surfaces and explore the opportunity to tune band edge energies of this and related semiconductors via electrostatic dipoles associated with chemisorbed ligands. We predict substantial shifts in band edge energies originating from both the induced dipole at the ligand/CdSe interface and the intrinsic dipole of the ligand. Building on important induced dipole contributions, we further show that, by changing the size and orientation of the ligand's intrinsic dipole moment via functionalization, we can control the direction and magnitude of the shifts of CdSe electronic levels. Our calculations suggest a general strategy for enabling new active semiconductor photocatalysts with both optimal opto-electronic, and photo- and electrochemical properties. PMID:22192078

  17. Increasing efficiency in intermediate band solar cells with overlapping absorptions

    NASA Astrophysics Data System (ADS)

    Krishna, Akshay; Krich, Jacob J.

    2016-07-01

    Intermediate band (IB) materials are promising candidates for realizing high efficiency solar cells. In IB photovoltaics, photons are absorbed in one of three possible electronic transitions—valence to conduction band, valence to intermediate band, or intermediate to conduction band. With fully concentrated sunlight, when the band gaps have been chosen appropriately, the highest efficiency IB solar cells require that these three absorptions be non-overlapping, so absorbed photons of fixed energy contribute to only one transition. The realistic case of overlapping absorptions, where the transitions compete for photons, is generally considered to be a source of loss. We show that overlapping absorptions can in fact lead to significant improvements in IB solar cell efficiencies, especially for IB that are near the middle of the band gap. At low to moderate concentration, the highest efficiency requires overlapping absorptions. We use the detailed-balance method and indicate how much overlap of the absorptions is required to achieve efficiency improvements, comparing with some known cases. These results substantially broaden the set of materials that can be suitable for high-efficiency IB solar cells.

  18. Band-edge lasing in Rh6G-doped dichromated gelatin at different excitations

    NASA Astrophysics Data System (ADS)

    Ying, Cui-Feng; Zhou, Wen-Yuan; Ye, Qing; Zhang, Xiao-Liang; Tian, Jian-Guo

    2010-11-01

    One-dimensional photonic crystal band-edge lasing at different excitations was studied experimentally by altering the excitation angle. We considered almost every condition including in-band, out-of-band and near the band edge while keeping the density of states unchanged. Holographic rhodamin 6G-doped dichromated gelatin was used for creating low-threshold photonic band-edge lasing (PBEL). Lasing actions excited near the high-energy and low-energy band edges were observed simultaneously, and their full widths at half maximum were different. The results show that the PBEL intensity and pump efficiency are sensitive to the excitation angle, enhanced obviously at the excitation near the band edge and suppressed distinctly in the band which agreed well with the theoretical prediction. We also demonstrated for the first time that active matters exist not only in the air voids but also in the high-index regions of the gelatin.

  19. Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier

    PubMed Central

    Ling, Zhi-Peng; Sakar, Soumya; Mathew, Sinu; Zhu, Jun-Tao; Gopinadhan, K.; Venkatesan, T.; Ang, Kah-Wee

    2015-01-01

    Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec). PMID:26667402

  20. Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier

    NASA Astrophysics Data System (ADS)

    Ling, Zhi-Peng; Sakar, Soumya; Mathew, Sinu; Zhu, Jun-Tao; Gopinadhan, K.; Venkatesan, T.; Ang, Kah-Wee

    2015-12-01

    Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec).

  1. Black Phosphorus Transistors with Near Band Edge Contact Schottky Barrier.

    PubMed

    Ling, Zhi-Peng; Sakar, Soumya; Mathew, Sinu; Zhu, Jun-Tao; Gopinadhan, K; Venkatesan, T; Ang, Kah-Wee

    2015-01-01

    Black phosphorus (BP) is a new class of 2D material which holds promise for next generation transistor applications owing to its intrinsically superior carrier mobility properties. Among other issues, achieving good ohmic contacts with low source-drain parasitic resistance in BP field-effect transistors (FET) remains a challenge. For the first time, we report a new contact technology that employs the use of high work function nickel (Ni) and thermal anneal to produce a metal alloy that effectively reduces the contact Schottky barrier height (ΦB) in a BP FET. When annealed at 300 °C, the Ni electrode was found to react with the underlying BP crystal and resulted in the formation of nickel-phosphide (Ni2P) alloy. This serves to de-pin the metal Fermi level close to the valence band edge and realizes a record low hole ΦB of merely ~12 meV. The ΦB at the valence band has also been shown to be thickness-dependent, wherein increasing BP multi-layers results in a smaller ΦB due to bandgap energy shrinkage. The integration of hafnium-dioxide high-k gate dielectric additionally enables a significantly improved subthreshold swing (SS ~ 200 mV/dec), surpassing previously reported BP FETs with conventional SiO2 gate dielectric (SS > 1 V/dec). PMID:26667402

  2. Electronic Band Structure and Sub-band-gap Absorption of Nitrogen Hyperdoped Silicon

    PubMed Central

    Zhu, Zhen; Shao, Hezhu; Dong, Xiao; Li, Ning; Ning, Bo-Yuan; Ning, Xi-Jing; Zhao, Li; Zhuang, Jun

    2015-01-01

    We investigated the atomic geometry, electronic band structure, and optical absorption of nitrogen hyperdoped silicon based on first-principles calculations. The results show that all the paired nitrogen defects we studied do not introduce intermediate band, while most of single nitrogen defects can introduce intermediate band in the gap. Considering the stability of the single defects and the rapid resolidification following the laser melting process in our sample preparation method, we conclude that the substitutional nitrogen defect, whose fraction was tiny and could be neglected before, should have considerable fraction in the hyperdoped silicon and results in the visible sub-band-gap absorption as observed in the experiment. Furthermore, our calculations show that the substitutional nitrogen defect has good stability, which could be one of the reasons why the sub-band-gap absorptance remains almost unchanged after annealing. PMID:26012369

  3. Room-Temperature Absorption Edge of InGaN/GaN Quantum Wells Characterized by Photoacoustic Measurement

    NASA Astrophysics Data System (ADS)

    Takeda, Yosuke; Takagi, Daigo; Sano, Tatsuji; Tabata, Shin; Kobayashi, Naoki; Shen, Qing; Toyoda, Taro; Yamamoto, Jun; Ban, Yuzaburo; Matsumoto, Kou

    2008-12-01

    The absorption edges of five periods of InxGa1-xN (3 nm)/GaN (15 nm) (x=0.07-0.23) quantum wells (QWs) are characterized by photoacoustic (PA) measurement at room temperature. The absorption edge is determined by differentiating the PA signal curve to obtain the inflection point on the assumption that the signal curve consists of Urbach tail in the low-energy region and Elliott's equation in the high-energy region. The constant absorption edge of GaN is observed at 3.4 eV and an absorption edge redshift with increasing In composition is observed for InGaN QWs. As a result, the Stokes shift increases with In composition and the highest shift of 435 meV is observed at x=0.23. From the energy calculation of optical transition in the InGaN/GaN QWs under an internal polarization field, the transition between the ground states confined in the well with a triangular potential causes a low-energy shift in the photoluminescence peak from the bulk band-gap energy, and the excited bound states whose wave functions are confined by the step-linear potential extending over the GaN barrier lead to the high-energy shift in the absorption edge.

  4. Automated Extraction of Absorption Bands from Reflectance Special

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Vale, L.; Mcintire, D.; Jones, J.

    1985-01-01

    A multiple high order derivative spectroscopy technique has been developed for deriving wavelength positions, half widths, and heights of absorption bands in reflectance spectra. The technique is applicable to laboratory spectra as well as medium resolution (100-200/cm) telescope or spacecraft spectra with moderate (few percent) noise. The technique permits absorption band positions to be detected with an accuracy of better than 3%, and often better than 1%. The high complexity of radiative transfer processes in diffusely reflected spectra can complicate the determination of absorption band positions. Continuum reflections, random illumination geometries within the material, phase angle effects, composite overlapping bands, and calibration uncertainties can shift apparent band positions by 20% from their actual positions or mask them beyond detection. Using multiple high order derivative analysis, effects of scattering continua, phase angle, and calibration (smooth features) are suppressed. Inflection points that characterize the positions and half widths of constituent bands are enhanced by the process and directly detected with relatively high sensitivity.

  5. Isoabsorption and spectrometric studies of optical absorption edge in Cu6AsS5I superionic crystal

    NASA Astrophysics Data System (ADS)

    Studenyak, I. P.; Kayla, M. I.; Kranjčec, M.; Kokhan, O. P.; Minets, Yu. V.

    2011-12-01

    Cu6AsS5I single crystals were grown using chemical vapour transport method. Two low-temperature phase transitions (PT) are observed from isoabsorption studies: a first-order PT at ТІ=153±1 K and a second-order PT in the temperature interval TІI=260-280 K. At low temperatures and high absorption levels an excitonic absorption band was revealed in the range of direct optical transitions. At Т>ТІ, the absorption edge has an exponential shape and a characteristic Urbach bundle is observed. The influence of the cationic P→As substitution on the parameters of the Urbach absorption edge, parameters of exciton-phonon interaction, and phase transitions temperatures are studied.

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

    PubMed Central

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

    2015-01-01

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

  7. Absorptivity of nitric oxide in the fundamental vibrational band

    NASA Astrophysics Data System (ADS)

    Holland, R. F.; Vasquez, M. C.; Beattie, W. H.; McDowell, R. S.

    1983-05-01

    From observations of the spectral absorbance of mixtures of nitric oxide in nitrogen at room temperature, an integrated absorptivity for the NO fundamental band of 137.3 + or - 4.6 per(sq cm atm) at 0 C is derived. The indicated uncertainty is the estimated maximum error.

  8. Absorption edge and the refractive index dispersion of carbon-nickel composite films at different annealing temperatures

    NASA Astrophysics Data System (ADS)

    Dalouji, Vali; Elahi, Seyed Mohammad; Solaymani, Shahram; Ghaderi, Atefeh

    2016-04-01

    In this paper, the optical properties of carbon-nickel films annealed at different temperatures 300, 500, 800 and 1000 ° C, with a special emphasis on the absorption edge, were investigated. The optical transmittance spectra in the wavelength range 300-1000nm were used to compute the absorption coefficient. The optical dispersion parameters were calculated according to Wemple and DiDomenico (WDD) single-oscillator model. Photoluminescence (PL) measurements of carbon-nickel films exhibit two main peaks at about 2.5 and 3.3eV which correspond to the fundamental indirect and direct gap, respectively. The field emission scanning electron microscopy (FESEM) showed that the absorption edge in the films was controlled by the nanoparticle size. The films annealed at 500 ° C have minimum indirect optical band gap and maximum disorder.

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

    NASA Technical Reports Server (NTRS)

    Singhroy, Vernon H.; Kruse, Fred A.

    1991-01-01

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

  10. Variation in optical-absorption edge in SiN{sub x} layers with silicon clusters

    SciTech Connect

    Efremov, M. D. Volodin, V. A.; Marin, D. V.; Arzhannikova, S. A.; Kamaev, G. N.; Kochubei, S. A.; Popov, A. A.

    2008-02-15

    Using optical methods, data on optical constants are obtained for silicon nitride films synthesized by plasma-chemical vapor deposition (PCVD). Models for calculating the permittivity in the model of inhomogeneous phase mixture of silicon and silicon nitride are considered. It is found that the optical-absorption edge (E{sub g}) and the photoluminescence peak shift to longer wavelengths with increasing nitrogen atomic fraction x in sin{sub x} films. When x approaches the value 4/3 characteristic for stoichiometric silicon nitride Si{sub 3}N{sub 4}, a nonlinear sharp increase in E{sub g} is observed. Using Raman scattering, Si-Si bonds are revealed, which confirms the direct formation of silicon clusters during the film deposition. The relation between the composition of nonstoichiometric silicon nitride films, values of permittivity, and the optical-band width is established for light transmission.

  11. 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.

  12. Planar Defect Modes Excited at the Band Edge of Three-dimensional Photonic Crystals

    NASA Astrophysics Data System (ADS)

    Iida, Masaru; Tani, Masahiko; Sakai, Kiyomi; Watanabe, Masayoshi; Kitahara, Hideaki; Tohme, Takuya; Wada Takeda, Mitsuo

    2004-09-01

    We experimentally and numerically studied planar defect modes excited at band-edge resonant mode frequencies in three-dimensional photonic crystals. We identified the observed peaks as the defect modes using the spectrum calculated at the defect layer. The spectrum also clarifies the difference between these modes and ordinary band-edge resonant modes. The calculated spatial distribution of the electric field in the defect modes shows that the defect modes have a characteristic field concentration in the band-edge resonant mode.

  13. Core-hole effects on theoretical electron-energy-loss near-edge structure and near-edge x-ray absorption fine structure of MgO

    NASA Astrophysics Data System (ADS)

    Mizoguchi, Teruyasu; Tanaka, Isao; Yoshiya, Masato; Oba, Fumiyasu; Ogasawara, Kazuyoshi; Adachi, Hirohiko

    2000-01-01

    First-principles molecular orbital calculations using model clusters are made in order to reproduce and interpret experimental electron-energy-loss near-edge structure and near-edge x-ray absorption fine structure of MgO at Mg K, L2,3 and O K edges. Ground-state calculations using a model cluster composed of 125 atoms and by a band-structure method are in good agreement, but they do not reproduce the experimental spectra satisfactory. They are well reproduced only by the cluster calculations for the Slater transition state, where a half-electron is removed from a core orbital and placed into the lowest unoccupied molecular orbital. The core-hole effect is therefore essential for theoretical reproduction of the spectral shapes. A large supercell is required to reproduce the experimental spectra when one uses a band-structure method. The origin of peaks appearing in the experimental spectra is interpreted in terms of orbital interactions using overlap-population diagrams. Some features of the spectra at different edges are pointed out to have common origins. Experimental spectra are aligned accordingly. The transition energies and qualitative features of experimental spectra are found to be reproduced even using a smaller cluster composed of 27 atoms, although some of fine structure is missing.

  14. Topologically trivial and nontrivial edge bands in graphene induced by irradiation

    NASA Astrophysics Data System (ADS)

    Yang, Mou; Cai, Zhi-Jun; Wang, Rui-Qiang; Bai, Yan-Kui

    2016-08-01

    We proposed a minimal model to describe the Floquet band structure of two-dimensional materials with light-induced resonant inter-band transition. We applied it to graphene to study the band features caused by the light irradiation. Linearly polarized light induces pseudo gaps (gaps are functions of wavevector), and circularly polarized light causes real gaps on the quasi-energy spectrum. If the polarization of light is linear and along the longitudinal direction of zigzag ribbons, flat edge bands appear in the pseudo gaps, and if it is in the lateral direction of armchair ribbons, curved edge bands can be found. For the circularly polarized cases, edge bands arise and intersect in the gaps of both types of ribbons. The edge bands induced by the circularly polarized light are helical and those by linearly polarized light are topologically trivial ones. The Chern number of the Floquet band, which reflects the number of pairs of helical edge bands in graphene ribbons, can be reduced into the winding number at resonance.

  15. Photodissociation of vibrationally excited water in the first absorption band

    NASA Astrophysics Data System (ADS)

    Weide, Klaus; Hennig, Steffen; Schinke, Reinhard

    1989-12-01

    We investigate the photodissociation of highly excited vibrational states of water in the first absorption band. The calculation includes an ab initio potential energy surface for the Östate and an ab initio X˜→Ã transition dipole function. The bending angle is fixed at the equilibrium value within the ground electronic state. Most interesting is the high sensitivity of the final vibrational distribution of OH on the initially prepared vibrational state of H2 O. At wavelengths near the onset of the absorption spectrum the vibrational state distribution can be qualitatively understood as a Franck-Condon mapping of the initial H2 O wave function. At smaller wavelengths final state interaction in the excited state becomes stronger and the distributions become successively broader. Our calculations are in satisfactory accord with recent measurements of Vander Wal and Crim.

  16. Epitaxy, phase separation and band-edge emission of spontaneously formed InGaN nanorods

    NASA Astrophysics Data System (ADS)

    De, Arpan; Shivaprasad, S. M.

    2016-09-01

    An In-flux dependent study of the nature of epitaxy, compositional phase separation and band-edge emission of spontaneously formed c-oriented InGaN nanorods on c-sapphire is performed. At higher In flux-rates, m-faceted thick nanorods (≈700 nm) form with two in-plane epitaxial orientations, and display compositional phases with In composition varying from 14 to 63%. In these rods, photo-luminescent (PL) emission is seen to originate only from the localized high-In phase (63%) that is embedded in the low-In (14%) InGaN matrix. As the In flux-rate is reduced, nanorods of smaller diameter (≈60 nm) and a coalesced nanorod network are formed, with In incorporation of 15% and 9%, respectively. These faceted, c-aligned thinner nanorods are of a single compositional phase and epitaxy and display room-temperature PL emission. Optical absorption and emission properties of these nanostructures follow Vegard’s law of band-gaps, and the observed bowing parameter and Stokes shifts correlate to the observed compositional inhomogeneity and carrier localization.

  17. Zero-coupling-gap degenerate band edge resonators in silicon photonics.

    PubMed

    Burr, Justin R; Reano, Ronald M

    2015-11-30

    Resonances near regular photonic band edges are limited by quality factors that scale only to the third power of the number of periods. In contrast, resonances near degenerate photonic band edges can scale to the fifth power of the number periods, yielding a route to significant device miniaturization. For applications in silicon integrated photonics, we present the design and analysis of zero-coupling-gap degenerate band edge resonators. Complex band diagrams are computed for the unit cell with periodic boundary conditions that convey characteristics of propagating and evanescent modes. Dispersion features of the band diagram are used to describe changes in resonance scaling in finite length resonators. Resonators with non-zero and zero coupling gap are compared. Analysis of quality factor and resonance frequency indicates significant reduction in the number of periods required to observe fifth power scaling when degenerate band edge resonators are realized with zero-coupling-gap. High transmission is achieved by optimizing the waveguide feed to the resonator. Compact band edge cavities with large optical field distribution are envisioned for light emitters, switches, and sensors. PMID:26698725

  18. 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.

  19. Optical absorption of nanoporous silicon: quasiparticle band gaps and absorption spectra

    NASA Astrophysics Data System (ADS)

    Shi, Guangsha; Kioupakis, Emmanouil

    2013-03-01

    Silicon is an earth-abundant material of great importance in semiconductors electronics, but its photovoltaic applications are limited by the low absorption coefficient in the visible due to its indirect band gap. One strategy to improve the absorbance is to perforate silicon with nanoscale pores, which introduce carrier scattering that enables optical transitions across the indirect gap. We used density functional and many-body perturbation theory in the GW approximation to investigate the electronic and optical properties of porous silicon for various pore sizes, spacings, and orientations. Our calculations include up to 400 atoms in the unit cell. We will discuss the connection of the band-gap value and absorption coefficient to the underlying nanopore geometry. The absorption coefficient in the visible range is found to be optimal for appropriately chosen nanopore size, spacing, and orientation. Our work allows us to predict porous-silicon structures that may have optimal performance in photovoltaic applications. This research was supported as part of CSTEC, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Computational resources were provided by the DOE NERSC facility.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  2. Effects of deformation on band-edge luminescence of hexagonal boron nitride single crystals

    NASA Astrophysics Data System (ADS)

    Watanabe, Kenji; Taniguchi, Takashi; Kuroda, Takashi; Kanda, Hisao

    2006-10-01

    The authors observed a drastic change in exciton-related luminescence in deformed hexagonal boron nitride single crystals. High quality single crystals that showed a free exciton luminescence band at 215nm were used as a starting material. They were pinched between aluminum plates and pressed with the tips of the first two fingers. The pressed crystals dominantly showed band-edge luminescence at the 227 instead of the 215nm band. The authors attribute this 227nm band to bound exciton luminescence caused by the stacking disorder produced by the mechanical deformation.

  3. Low-threshold photonic-band-edge laser using iron-nail-shaped rod array

    SciTech Connect

    Choi, Jae-Hyuck; No, You-Shin; Hwang, Min-Soo; Jeong, Kwang-Yong; Park, Hong-Gyu E-mail: hgpark@korea.ac.kr; Kwon, Soon-Yong; Yang, Jin-Kyu E-mail: hgpark@korea.ac.kr; Kwon, Soon-Hong

    2014-03-03

    We report the experimental demonstration of an optically pumped rod-type photonic-crystal band-edge laser. The structure consists of a 20 × 20 square lattice array of InGaAsP iron-nail-shaped rods. A single-mode lasing action is observed with a low threshold of ∼90 μW and a peak wavelength of 1451.5 nm at room temperature. Measurements of the polarization-resolved mode images and lasing wavelengths agree well with numerical simulations, which confirm that the observed lasing mode originates from the first Γ-point transverse-electric-like band-edge mode. We believe that this low-threshold band-edge laser will be useful for the practical implementation of nanolasers.

  4. Antarctic krill under sea ice: elevated abundance in a narrow band just south of ice edge.

    PubMed

    Brierley, Andrew S; Fernandes, Paul G; Brandon, Mark A; Armstrong, Frederick; Millard, Nicholas W; McPhail, Steven D; Stevenson, Peter; Pebody, Miles; Perrett, James; Squires, Mark; Bone, Douglas G; Griffiths, Gwyn

    2002-03-01

    We surveyed Antarctic krill (Euphausia superba) under sea ice using the autonomous underwater vehicle Autosub-2. Krill were concentrated within a band under ice between 1 and 13 kilometers south of the ice edge. Within this band, krill densities were fivefold greater than that of open water. The under-ice environment has long been considered an important habitat for krill, but sampling difficulties have previously prevented direct observations under ice over the scale necessary for robust krill density estimation. Autosub-2 enabled us to make continuous high-resolution measurements of krill density under ice reaching 27 kilometers beyond the ice edge. PMID:11884754

  5. Effects of surface oxide formation on germanium nanowire band-edge photoluminescence

    SciTech Connect

    Minaye Hashemi, Fatemeh Sadat; Laboratoire des Materiaux Semiconducteurs, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne ; Thombare, Shruti; Brongersma, Mark L.; Morral, Anna Fontcuberta i; McIntyre, Paul C.; Geballe Laboratory for Advanced Materials, Stanford University, Stanford, California 94305

    2013-06-24

    The effect of intentional surface oxide formation on band-edge photoluminescence (PL) of Ge nanowires was investigated. Thermal oxidation in molecular O{sub 2} was used to produce a surface oxide layer on assemblies of single crystal nanowires grown by the vapor-liquid-solid method. With increasing oxidation of the wires, the band-edge PL associated with the indirect gap transition becomes more intense. X-ray photoelectron spectroscopy confirms the formation of an increasingly GeO{sub 2}-like surface oxide under annealing conditions that enhance the indirect-gap PL, consistent with surface oxide passivation of nonradiative recombination centers initially present on the nanowire surface.

  6. Propane absorption band intensities and band model parameters from 680 to 1580/cm at 296 and 200 K

    NASA Technical Reports Server (NTRS)

    Giver, L. P.; Valero, F. P. J.; Varanasi, P.

    1984-01-01

    Band intensities and profiles have been measured for the propane absorption bands from 680 to 1580/cm at 296 and 200 K. This work was stimulated by the discovery of several propane bands in the spectrum of Titan by the Voyager 1 spacecraft. The low temperature laboratory data show that the bands become narrower and the Q branches of the bands somewhat stronger than they are at room temperature. Random band model parameters were determined over the entire region from the 42 spectra obtained at room temperature.

  7. Sensitivity of Sentinel-2 Red-Edge Bands to Leaf Chlorophyll Concentration in Winter Wheat

    NASA Astrophysics Data System (ADS)

    Vincini, Massimo; Amaducci, Stefano; Frazzi, Ermes

    2012-04-01

    The present work addresses the comparison between the sensitivity of several narrow-band and broad-band vegetation indices (VI) to leaf chlorophyll concentration at the canopy scale in winter wheat field trials with different nitrogen fertilization levels. Spectral signatures were collected on three dates (Feekes growth stages 5-6-9) over experimental plots with a portable spectroradiometer (ASD FieldSpec HH), along with Minolta SPAD measures of leaf optical thickness as a proxy of leaf chlorophyll concentration. Considered broad-band indices included classical slope-based VI (i.e.: NDVI, SR and OSAVI) and some indices incorporating green reflectance (i.e. Green NDVI, Green SR, CVI and MTVI), whereas narrow-band indices included VI specifically proposed as leaf chlorophyll estimators at the canopy scale (i.e. MCARI/OSAVI, TCARI/OSAVI, TCI/OSAVI, NOAC, REIP and MTCI). Broad-band VI were obtained from average reflectance in spectral ranges corresponding to SPOT HRG bands and from average reflectance in Sentinel-2 visible and NIR bands whereas narrow-band VI were obtained from reflectance at the original spectral resolution of the spectroradiometer and from average reflectance in Sentinel-2 Red-Edge bands. Among VI obtained from Sentinel-2 bands REIP and MTCI indices were the best narrow-band estimators of winter wheat leaf chlorophyll concentration, whereas CVI was the best estimator among broad-band VI.

  8. Enhanced dual-band infrared absorption in a Fabry-Perot cavity with subwavelength metallic grating.

    PubMed

    Kang, Guoguo; Vartiainen, Ismo; Bai, Benfeng; Turunen, Jari

    2011-01-17

    The performance of infrared (IR) dual-band detector can be substantially improved by simultaneously increasing IR absorptions for both sensor bands. Currently available methods only provide absorption enhancement for single spectral band, but not for the dual-band. The Fabry-Perot (FP) cavity generates a series of resonances in multispectral bands. With this flexibility, we introduced a novel type of dual-band detector structure containing a multilayer FP cavity with two absorbing layers and a subwavelength-period grating mirror, which is capable of simultaneously enhancing the middle wave infrared (MWIR) and the long wave infrared (LWIR) detection. Compared with the bare-absorption-layer detector (common dual-band detector), the optimized FP cavity can provide about 13 times and 17 times absorption enhancement in LWIR and MWIR bands respectively. PMID:21263618

  9. 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.

  10. Photoelectron Experiments and Studies of X-Ray Absorption Near Edge Structure in Alkaline-Earth and Rare - Fluorides.

    NASA Astrophysics Data System (ADS)

    Gao, Yuan

    Alkaline-earth fluorides and rare-earth trifluorides possess technological importance for applications in multi -layer electronic device structures and opto-electronic devices. Interfaces between thin films of YbF _3 and Si(111) substrates were studied by photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. Results of YbF_3 /Si(111) were compared with those of TmF _3/Si(111). While electrons in the Si valence band are prevented from occupying the empty 4f levels in TmF_3 at the interface by the on -site Coulomb repulsion energy, the charge transfer from Si to YbF_3 is possible because the totally filled 4f states in Yb still lie below the Si valence band maximum. The theory of x-ray absorption near edge structure (XANES) is incomplete except for a few particularly simple special cases. A Bragg reflection model was developed to qualitatively explain the oscillations in XANES, in terms of the scattering of the photoelectron wave between families of lattice planes as set out by the Bragg condition for backscattering. The model was found to represent the data for systems with nearly free electron like conduction bands reasonably well. High resolution CaF_2 fluorine K edge XANES was used as a prototype to understand XANES in more depth on systems with strong core hole effects. Unlike previous work which involved multiple scattering cluster calculations that include only short range order effects, both the long range order and the symmetry breaking core holes are included in a new bandstructure approach in which the core hole is treated with a supercell technique. A first principles calculation with the use of pseudopotentials successfully reproduced all the main features of the first 15 eV of the fluorine K edge in CaF_2 which had not been explained with the cluster calculations. A comparison of the theoretical and experimental fluorine K edges in CaF_2 and BaF _2 was used to identify the structure related features. The possibility

  11. Absolute Instability near the Band Edge of Traveling-Wave Amplifiers

    NASA Astrophysics Data System (ADS)

    Hung, D. M. H.; Rittersdorf, I. M.; Zhang, P.; Chernin, D.; Lau, Y. Y.; Antonsen, T. M.; Luginsland, J. W.; Simon, D. H.; Gilgenbach, R. M.

    2015-09-01

    Applying the Briggs-Bers "pole-pinch" criterion to the exact transcendental dispersion relation of a dielectric traveling wave tube (TWT), we find that there is no absolute instability regardless of the beam current. We extend this analysis to the circuit band edges of a linear beam TWT by approximating the circuit mode as a hyperbola in the frequency-wave-number (ω -k ) plane and consider the weak coupling limit. For an operating mode whose group velocity is in the same direction as the beam mode, we find that the lower band edge is not subjected to absolute instability. At the upper band edge, we find a threshold beam current beyond which absolute instability is excited. The nonexistence of absolute instability in a linear beam TWT and the existence in a gyrotron TWT, both at the lower band edge, is contrasted. The general study given here is applicable to some contemporary TWTs such as metamaterial-based and advanced Smith-Purcell TWTs.

  12. Absolute Instability near the Band Edge of Traveling-Wave Amplifiers.

    PubMed

    Hung, D M H; Rittersdorf, I M; Zhang, P; Chernin, D; Lau, Y Y; Antonsen, T M; Luginsland, J W; Simon, D H; Gilgenbach, R M

    2015-09-18

    Applying the Briggs-Bers "pole-pinch" criterion to the exact transcendental dispersion relation of a dielectric traveling wave tube (TWT), we find that there is no absolute instability regardless of the beam current. We extend this analysis to the circuit band edges of a linear beam TWT by approximating the circuit mode as a hyperbola in the frequency-wave-number (ω-k) plane and consider the weak coupling limit. For an operating mode whose group velocity is in the same direction as the beam mode, we find that the lower band edge is not subjected to absolute instability. At the upper band edge, we find a threshold beam current beyond which absolute instability is excited. The nonexistence of absolute instability in a linear beam TWT and the existence in a gyrotron TWT, both at the lower band edge, is contrasted. The general study given here is applicable to some contemporary TWTs such as metamaterial-based and advanced Smith-Purcell TWTs. PMID:26430996

  13. The use of bulk states to accelerate the band edge statecalculation of a semiconductor quantum dot

    SciTech Connect

    Vomel, Christof; Tomov, Stanimire Z.; Wang, Lin-Wang; Marques,Osni A.; Dongarra, Jack J.

    2006-05-10

    We present a new technique to accelerate the convergence of the folded spectrum method in empirical pseudopotential band edge state calculations for colloidal quantum dots. We use bulk band states of the materials constituent of the quantum dot to construct initial vectors and a preconditioner. We apply these to accelerate the convergence of the folded spectrum method for the interior states at the top of the valence and the bottom of the conduction band. For large CdSe quantum dots, the number of iteration steps until convergence decreases by about a factor of 4 compared to previous calculations.

  14. Evaluating the impact of red-edge band from Rapideye image for classifying insect defoliation levels

    NASA Astrophysics Data System (ADS)

    Adelabu, Samuel; Mutanga, Onisimo; Adam, Elhadi

    2014-09-01

    The prospect of regular assessments of insect defoliation using remote sensing technologies has increased in recent years through advances in the understanding of the spectral reflectance properties of vegetation. The aim of the present study was to evaluate the ability of the red edge channel of Rapideye imagery to discriminate different levels of insect defoliation in an African savanna by comparing the results of obtained from two classifiers. Random Forest and Support vector machine classification algorithms were applied using different sets of spectral analysis involving the red edge band. Results show that the integration of information from red edge increases classification accuracy of insect defoliation levels in all analysis performed in the study. For instance, when all the 5 bands of Rapideye imagery were used for classification, the overall accuracies increases about 19% and 21% for SVM and RF, respectively, as opposed to when the red edge channel was excluded. We also found out that the normalized difference red-edge index yielded a better accuracy result than normalized difference vegetation index. We conclude that the red-edge channel of relatively affordable and readily available high-resolution multispectral satellite data such as Rapideye has the potential to considerably improve insect defoliation classification especially in sub-Saharan Africa where data availability is limited.

  15. Shallow electron traps in alkali halide crystals: Mollwo-Ivey relations of the optical absorption bands

    NASA Astrophysics Data System (ADS)

    Ziraps, Valters

    2001-03-01

    Evidences are given that two classes of the transient IR- absorption bands: (a) with max. at 0.27-0.36 eV in NaCl, KCl, KBr, KI and RbCl (due to shallow electron traps according G. Jacobs or due to bound polarons according E.V. Korovkin and T.A. Lebedkina) and (b) with max. at 0.15-0.36 eV in NaI, NaBr, NaCl:I, KCl:I, RbCl:I and RbBr:I (due to on-center STE localized at iodine dimer according M. Hirai and collaborators) are caused by the same defect- atomic alkali impurity center [M+]c0e- (electron e- trapped by a substitutional smaller size alkali cation impurity [M+]c0). The Mollwo-Ivey plots (for the transient IR-absorption bands) of the zero-phonon line energy E0 (for NaCl, KCl, KBr, RbCl and NaBr, KCl:I) and/or the low-energy edge valued E0 (for NaI, RbCl:I, RbBr:I) versus anion-cation distance (d) evidence that two types of the [M+]c0e- centers are predominant: (a) [Na+]c0e- in the KX and RbX host crystals with the relation E0approximately equals 6.15/d2.74, (b) [Li+]c03- in the NaX host crystals - E0approximately equals 29.4/d4.72. The Mollwo-Ivey relation E0approximately equals 18.36/d(superscript 2.70 is fulfilled as well for the F' band in NaCl, KCl, KBr, KI, RbCl, RbI if we use the F' center optical binding energy values E0.

  16. Shot noise of the edge transport in the inverted band HgTe quantum wells

    NASA Astrophysics Data System (ADS)

    Tikhonov, E. S.; Shovkun, D. V.; Khrapai, V. S.; Kvon, Z. D.; Mikhailov, N. N.; Dvoretsky, S. A.

    2015-05-01

    We investigate the current noise in HgTe-based quantum wells with an inverted band structure in the regime of disordered edge transport. Consistent with previous experiments, the edge resistance strongly exceeds h/ e 2 and weakly depends on the temperature. The shot noise is well below the Poissonian value and characterized by the Fano factor with gate voltage and sample-to-sample variations in the range 0.1 < F < 0.3. Given the fact that our devices are shorter than the most pessimistic estimate of the ballistic dephasing length, these observations exclude the possibility of one-dimensional helical edge transport. Instead, we suggest that a disordered multi-mode conduction is responsible for the edge transport in our experiment.

  17. Electronic structure investigation of highly compressed aluminum with K edge absorption spectroscopy.

    PubMed

    Benuzzi-Mounaix, A; Dorchies, F; Recoules, V; Festa, F; Peyrusse, O; Levy, A; Ravasio, A; Hall, T; Koenig, M; Amadou, N; Brambrink, E; Mazevet, S

    2011-10-14

    The electronic structure evolution of highly compressed aluminum has been investigated using time resolved K edge x-ray absorption spectroscopy. A long laser pulse (500 ps, I(L)≈8×10(13) W/cm(2)) was used to create a uniform shock. A second ps pulse (I(L)≈10(17)  W/cm(2)) generated an ultrashort broadband x-ray source near the Al K edge. The main target was designed to probe aluminum at reshocked conditions up to now unexplored (3 times the solid density and temperatures around 8 eV). The hydrodynamical conditions were obtained using rear side visible diagnostics. Data were compared to ab initio and dense plasma calculations, indicating potential improvements in either description. This comparison shows that x-ray-absorption near-edge structure measurements provide a unique capability to probe matter at these extreme conditions and severally constrains theoretical approaches currently used. PMID:22107398

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

    NASA Astrophysics Data System (ADS)

    Mantouvalou, I.; Witte, K.; Martyanov, W.; Jonas, A.; Grötzsch, D.; Streeck, C.; Löchel, H.; Rudolph, I.; Erko, A.; Stiel, H.; Kanngießer, B.

    2016-05-01

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

  19. Experimental and theoretical investigation of the conduction band edge of GaNxP1-x

    NASA Astrophysics Data System (ADS)

    Güngerich, M.; Klar, P. J.; Heimbrodt, W.; Weiser, G.; Geisz, J. F.; Harris, C.; Lindsay, A.; O'Reilly, E. P.

    2006-12-01

    We show that a two-level band-anticrossing (BAC) model fails to describe the evolution of N-related states in GaNxP1-x . Band structure calculations prove that a two-level model describes these states in ordered GaNP supercells. Photocurrent measurements support a BAC-related blueshift of the GaP-like direct band gap in disordered GaNP, but calculations and electromodulated absorption and pressure studies show that the wide energy distribution of the lower-lying N-related states leads to the anticrossing interaction involving many N levels in disordered GaNP.

  20. Multiwavelength anomalous diffraction analysis at the M absorption edges of uranium

    PubMed Central

    Liu, Yee; Ogata, Craig M.; Hendrickson, Wayne A.

    2001-01-01

    The multiwavelength anomalous diffraction (MAD) method for phase evaluation is now widely used in macromolecular crystallography. Successful MAD structure determinations have been carried out at the K or L absorption edges of a variety of elements. In this study, we investigate the anomalous scattering properties of uranium at its MIV (3.326 Å) and MV (3.490 Å) edge. Fluorescence spectra showed remarkably strong anomalous scattering at these edges (f′ = −70e, f′′ = 80e at the MIV edge and f′ = −90e, f′′ = 105e at the MV edge), many times higher than from any anomalous scatterers used previously for MAD phasing. However, the large scattering angles and high absorption at the low energies of these edges present some difficulties not found in typical crystallographic studies. We conducted test experiments at the MIV edge with crystals of porcine elastase derivatized with uranyl nitrate. A four-wavelength MAD data set complete to 3.2-Å Bragg spacings was collected from a single small frozen crystal. Analysis of the data yielded satisfactory phase information (average difference of 0ϕT − 0ϕA for replicated determinations is 32°) and produced an interpretable electron-density map. Our results demonstrate that it is practical to measure macromolecular diffraction data at these edges with current instrumentation and that phase information of good accuracy can be extracted from such experiments. We show that such experiments have potential for the phasing of very large macromolecular assemblages. PMID:11526210

  1. Absorption coefficients and band strengths for the 703 nm and 727 bands of methane at 77 K

    SciTech Connect

    O`Brien, J.J.; Singh, K.

    1996-12-31

    The technique of intracavity laser spectroscopy has been used to obtain methane absorption spectra for the vibrational overtone bands that occur around 703 nm and 727 nm. Absorption coefficients for the 690-742 nm range have been obtained for a sample temperature of 77 K at a spectral resolution of <0.02 cm{sup -1}. A new method of data analysis is utilized in obtaining the results. It involves deconvolving the many ILS spectral profiles that comprise the absorption bands and summing the results. Values averaged over 1 cm{sup -1} and 1 {Angstrom} intervals are provided. Band strengths also are obtained. The total intensities of the 703 and 727 nm bands are in reasonable agreement with previous laboratory determinations which were obtained for relatively high pressures of methane at room temperature using lower spectral resolution. The methane bands appear in the reflected sunlight spectra from the outer planets. Results averaged over 1 nm intervals are compared with other laboratory studies and with those derived from observations of the outer planets. The band profiles differ considerably from other laboratory results but are in good accord with the planetary observations. Laboratory spectra of methane at appropriate conditions are required for the proper interpretation of the observational data. Absorption spectra can provide some of the most sensitive diagnostic data on the atmospheres of those bodies.

  2. 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.

  3. Band-edge lasing and miniband lasing in 1-D dual-periodic photonic crystal

    NASA Astrophysics Data System (ADS)

    Ying, Cui-Feng; Zhou, Wen-Yuan; Li, Yi; Ye, Qing; Zhang, Chun-Ping; Tian, Jian-Guo

    2012-06-01

    Herein, we report two different dual-periodic Photonic Crystals (PCs) in dichromated gelatin emulsion which are fabricated by four-beam holography and double-exposure holography. The minibands with high Q-factors have been evidently located in both two structures. By taking into account the non-uniform distribution of material, the numerical results agree quite well with the experimental results. We also compared the band-edge lasing in single-periodic PC and miniband lasing in Moiré dual-periodic PC. Due to extremely flat dispersion and large mode volume of the miniband, high optical conversion efficiency in miniband lasing is achieved as compared with that of band-edge lasing. Such effect may provide potential applications in low-threshold lasers and ultra-sensitive fluorescent probes in biological assays.

  4. Near band edge emission characteristics of sputtered nano-crystalline ZnO films

    NASA Astrophysics Data System (ADS)

    Kunj, Saurabh; Sreenivas, K.

    2016-05-01

    Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

  5. Removal of OH Absorption Bands Due to Pyrohydrolysis Reactions in Fluoride-Containing Borosilicate Glasses

    NASA Astrophysics Data System (ADS)

    Kobayashi, Keiji

    1997-05-01

    The purpose of this study is to decrease and to remove OH ions and H2O in borosilicate glasses. Fluoride-containing borosilicate glasses followed by dry-air-bubbling showed the significant decrease of OH absorption bands around 3500 cm-1. The decrease of OH absorption bands was elucidated by the use of pyrohydrolysis reactions in these glasses where fluoride ions react with OH ions or H2O during melting. The rates of the decrease of OH absorption bands substantially depend on high valence cations of fluorides. Particularly, the decrease rates of OH absorption coefficients were in the order of ZrF4-containing glass>AlF3-containing glass>ZnF2-containing glass. ZrF4-containing glass treated by dry-air-bubbling showed a good capability to remove OH absorption band. Fluoride-containing glasses showed the low flow point in comparison with fluoride-free glasses.

  6. The effect of spin-orbit coupling in band structure and edge states of bilayer graphene

    SciTech Connect

    Sahdan, Muhammad Fauzi; Darma, Yudi

    2015-04-16

    Topological insulators are predicted to be useful ranging from spintronics to quantum computation. Graphene was first predicted to be the precursor of topological insulator by Kane-Mele. They developed a Hamiltonian model to describe the gap opening in graphene. In this work, we investigate the band structure of bilayer grapheme and also its edge states by using this model with analytical approach. The results of our calculation show that the gap opening occurs at K and K’ point in bilayer graphene.In addition, a pair of gapless edge modes occurs both in the zigzag and arm-chair configurations are no longer exist. There are gap created at the edge even though thery are very small.

  7. Experimental study of absorption band controllable planar metamaterial absorber using asymmetrical snowflake-shaped configuration

    NASA Astrophysics Data System (ADS)

    Huang, Yongjun; Tian, Yiran; Wen, Guangjun; Zhu, Weiren

    2013-05-01

    In this paper, we systematically discuss a novel planar metamaterial absorber (PMA) based on asymmetrical snowflake-shaped resonators, which can exhibit two distinctly different absorption states, single- and dual-band absorptions, by controlling the branch lengths of the proposed resonators. Numerical simulations and experimental measurements are employed to investigate these two kinds of absorption characteristic in an X-band rectangular waveguide. Both results indicate that such a PMA exhibits a wide range of controllable operating frequencies for the single- and dual-band conditions. The proposed PMA is simple and easy to make, and it has wide applications in the fields of stealth technologies, thermal detectors, and imaging.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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.

  10. A high resolution x-ray fluorescence spectrometer for near edge absorption studies

    SciTech Connect

    Stojanoff, V.; Hamalainen, K.; Siddons, D.P.; Hastings, J.B.; Berman, L.E.; Cramer, S.; Smith, G.

    1991-01-01

    A high resolution fluorescence spectrometer using a Johann geometry in a back scattering arrangement was developed. The spectrometer, with a resolution of 0.3 eV at 6.5 keV, combined with an incident beam, with a resolution of 0.7 eV, form the basis of a high resolution instrument for measuring x-ray absorption spectra. The advantages of the instrument are illustrated with the near edge absorption spectrum of dysprosium nitrate. 10 refs., 4 figs.

  11. A high resolution x-ray fluorescence spectrometer for near edge absorption studies

    SciTech Connect

    Stojanoff, V.; Hamalainen, K.; Siddons, D.P.; Hastings, J.B.; Berman, L.E.; Cramer, S.; Smith, G.

    1991-12-31

    A high resolution fluorescence spectrometer using a Johann geometry in a back scattering arrangement was developed. The spectrometer, with a resolution of 0.3 eV at 6.5 keV, combined with an incident beam, with a resolution of 0.7 eV, form the basis of a high resolution instrument for measuring x-ray absorption spectra. The advantages of the instrument are illustrated with the near edge absorption spectrum of dysprosium nitrate. 10 refs., 4 figs.

  12. 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

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

    PubMed

    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/cm(3) sensitivity, sufficient for detecting the density corresponding to a single nanoparticle. PMID:26960695

  14. Oscillator strength of the peptide bond {pi}* resonances at all relevant x-ray absorption edges

    SciTech Connect

    Kummer, K.; Vyalikh, D. V.; Molodtsov, S. L.; Sivkov, V. N.; Nekipelov, S. V.; Maslyuk, V. V.; Mertig, I.; Blueher, A.; Mertig, M.; Bredow, T.

    2009-10-15

    Absolute x-ray absorption cross sections of a regular bacterial surface-layer protein deposited on a naturally oxidized silicon substrate were determined experimentally. Upon separation of the partial cross sections of the three relevant 1s absorption edges, the oscillator strengths of the 1s{yields}{pi}* excitations within the peptide-backbone unit were extracted. Comparison with results of first-principles calculations revealed their close correlation to the topology of {pi}{sub peptide}* orbitals of the peptide backbone.

  15. Multiple-scattering calculations of the uranium L3-edge x-ray-absorption near-edge structure

    NASA Astrophysics Data System (ADS)

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

    1995-11-01

    A theoretical study of the uranium L3-edge x-ray absorption near-edge structure (XANES) is presented for several uranium compounds, including oxides, intermetallics, uranyl fluoride, and α-uranium. Calculations were performed using feff6, an ab initio multiple-scattering (MS) code that includes the most important features of current theories. The results, which account for both the fine structure χ and the atomiclike background μ0 of the absorption coefficient μ, 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 UO2, 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 (UO2+2) compounds ~=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.

  16. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra.

    PubMed

    Rossi, G; d'Acapito, F; Amidani, L; Boscherini, F; Pedio, M

    2016-09-14

    We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure. PMID:27510989

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  18. 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.

  19. 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.

  20. Observation of temperature dependence of the IR hydroxyl absorption bands in silica optical fiber

    NASA Astrophysics Data System (ADS)

    Yu, Li; Bonnell, Elizabeth; Homa, Daniel; Pickrell, Gary; Wang, Anbo; Ohodnicki, P. R.; Woodruff, Steven; Chorpening, Benjamin; Buric, Michael

    2016-07-01

    This study reports on the temperature dependent behavior of silica based optical fibers upon exposure to high temperatures in hydrogen and ambient air. The hydroxyl absorption bands in the wavelength range of 1000-2500 nm of commercially available multimode fibers with pure silica and germanium doped cores were examined in the temperature range of 20-800 °C. Two hydroxyl-related infrared absorption bands were observed: ∼2200 nm assigned to the combination of the vibration mode of Si-OH bending and the fundamental hydroxyl stretching mode, and ∼1390 nm assigned to the first overtone of the hydroxyl stretching. The absorption in the 2200 nm band decreased in intensity, while the 1390 nm absorption band shifted to longer wavelengths with an increase in temperature. The observed phenomena were reversible with temperature and suspected to be due, in part, to the conversion of the OH spectral components into each other and structural relaxation.

  1. Position and Confidence Limits of an Extremum: The Determination of the Absorption Maximum in Wide Bands.

    ERIC Educational Resources Information Center

    Heilbronner, Edgar

    1979-01-01

    Discusses the determination of the position of the absorption maximum in wide bands as well as the confidence limits for such calculations. A simple method, suited for pocket calculators, for the numerical evaluation of these calculations is presented. (BB)

  2. Resonant diffraction in stishovite near the K absorption edge of silicon

    SciTech Connect

    Dmitrienko, V. E.; Ovchinnikova, E. N.

    2011-05-15

    The X-ray resonant diffraction in a stishovite crystal near the K absorption edge of silicon (E{sub K} = 1839 eV) is studied theoretically. For such a long wavelength, the only possible Bragg reflection is the 100 reflection, which is forbidden by the space group of the crystal. It can be excited solely due to anisotropy of the X-ray scattering amplitude. The crystal symmetry is used to determine the polarization and azimuthal dependence of the reflection intensity. Since this reflection is single, it can be detected upon diffraction from a powder, which substantially widens the possibilities of investigations. The numerical calculations of the energy dependences of the forbidden reflection intensity and the absorption coefficient demonstrate that the dipole-quadrupole, quadrupole-quadrupole, and dipole-octupole contributions to the resonant diffraction and absorption are small and that the dipole-dipole contribution is the most important one.

  3. HAC: Band Gap, Photoluminescence, and Optical/Near-Infrared Absorption

    NASA Technical Reports Server (NTRS)

    Witt, Adolf N.; Ryutov, Dimitri; Furton, Douglas G.

    1996-01-01

    We report results of laboratory measurements which illustrate the wide range of physical properties found among hydrogenated amorphous carbon (HAC) solids. Within this range, HAC can match quantitatively the astronomical phenomena ascribed to carbonaceous coatings on interstellar grains. We find the optical band gap of HAC to be well correlated with other physical properties of HAC of astronomical interest, and conclude that interstellar HAC must be fairly hydrogen-rich with a band gap of E(sub g) is approx. greater than 2.0 eV.

  4. Cause of absorption band shift of disperse red-13 attached on silica spheres

    NASA Astrophysics Data System (ADS)

    Kim, Byoung-Ju; Kim, Hyung-Deok; Kim, Na-Rae; Bang, Byeong-Gyu; Park, Eun-Hye; Kang, Kwang-Sun

    2015-08-01

    A reversible color change and large absorption band shift have been observed for the disperse red-13 (DR-13) attached on the surface of the monodisperse silica spheres. Two step synthetic processes including urethane bond formation and hydrolysis-condensation reactions were used to attach the DR-13 on the surface of the silica spheres. After the reaction, the characteristic absorption peak at 2270 cm-1 representing the -N=C=O asymmetric stretching vibration disappeared, and the a new absorption peak at 1700 cm-1 corresponding the C=O stretching vibration appeared. A visual and reversible color change was observed before and after wetting in alcohol. Although the absorption peak of DR-13 in alcohol is at 510 nm, the absorption peak shifts to 788 nm when it is dried. The absorption peak shifts to 718 nm when it is wetted in alcohol. This result can be explained by the formation of intramolecular charge transfer band.

  5. 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

  6. Atmospheric absorption of high frequency noise and application to fractional-octave bands

    NASA Technical Reports Server (NTRS)

    Shields, F. D.; Bass, H. E.

    1977-01-01

    Pure tone sound absorption coefficients were measured at 1/12 octave intervals from 4 to 100 KHz at 5.5K temperature intervals between 255.4 and 310.9 K and at 10 percent relative humidity increments between 0 percent and saturation in a large cylindrical tube (i.d., 25.4 cm; length, 4.8 m). Special solid-dielectric capacitance transducers, one to generate bursts of sound waves and one to terminate the sound path and detect the tone bursts, were constructed to fit inside the tube. The absorption was measured by varying the transmitter receiver separation from 1 to 4 m and observing the decay of multiple reflections or change in amplitude of the first received burst. The resulting absorption was compared with that from a proposed procedure for computing sound absorption in still air. Absorption of bands of noise was numerically computed by using the pure tone results. The results depended on spectrum shape, on filter type, and nonlinearly on propagation distance. For some of the cases considered, comparison with the extrapolation of ARP-866A showed a difference as large as a factor of 2. However, for many cases, the absorption for a finite band was nearly equal to the pure tone absorption at the center frequency of the band. A recommended prediction procedure is described for 1/3 octave band absorption coefficients.

  7. Evidence for sulphur implantation in Europa's UV absorption band

    NASA Technical Reports Server (NTRS)

    Lane, A. L.; Nelson, R. M.; Matson, D. L.

    1981-01-01

    The UV spectral characteristics of the Galilean satellites are investigated (using data from the International Ultraviolet Explorer (IUE) spacecraft) as a function of the orbital position, large-scale areal variability, and temporal dynamics. The discovery of an absorption feature at 280 nm in Europa's reflection spectrum is reported and observations show that the absorption is strongest on the trailing hemisphere (central longitude 270 degrees). The feature resembles SO2 and seems to result from S-O bond formation between deeply implanted sulphur atoms and the adjacent damaged water-ice-lattice. The sulphur supposedly comes from energetic (hundreds of keV) sulphur ions that are present in the Jovian magnetosphere. An appropriate equilibrium condition can be found to match the observed spectral data if sputtering erosion occurs at no greater than approximately 20 meters per one billion years.

  8. Biologically inspired band-edge laser action from semiconductor with dipole-forbidden band-gap transition

    PubMed Central

    Wang, Cih-Su; Liau, Chi-Shung; Sun, Tzu-Ming; Chen, Yu-Chia; Lin, Tai-Yuan; Chen, Yang-Fang

    2015-01-01

    A new approach is proposed to light up band-edge stimulated emission arising from a semiconductor with dipole-forbidden band-gap transition. To illustrate our working principle, here we demonstrate the feasibility on the composite of SnO2 nanowires (NWs) and chicken albumen. SnO2 NWs, which merely emit visible defect emission, are observed to generate a strong ultraviolet fluorescence centered at 387 nm assisted by chicken albumen at room temperature. In addition, a stunning laser action is further discovered in the albumen/SnO2 NWs composite system. The underlying mechanism is interpreted in terms of the fluorescence resonance energy transfer (FRET) from the chicken albumen protein to SnO2 NWs. More importantly, the giant oscillator strength of shallow defect states, which is served orders of magnitude larger than that of the free exciton, plays a decisive role. Our approach therefore shows that bio-materials exhibit a great potential in applications for novel light emitters, which may open up a new avenue for the development of bio-inspired optoelectronic devices. PMID:25758749

  9. Biologically inspired band-edge laser action from semiconductor with dipole-forbidden band-gap transition

    NASA Astrophysics Data System (ADS)

    Wang, Cih-Su; Liau, Chi-Shung; Sun, Tzu-Ming; Chen, Yu-Chia; Lin, Tai-Yuan; Chen, Yang-Fang

    2015-03-01

    A new approach is proposed to light up band-edge stimulated emission arising from a semiconductor with dipole-forbidden band-gap transition. To illustrate our working principle, here we demonstrate the feasibility on the composite of SnO2 nanowires (NWs) and chicken albumen. SnO2 NWs, which merely emit visible defect emission, are observed to generate a strong ultraviolet fluorescence centered at 387 nm assisted by chicken albumen at room temperature. In addition, a stunning laser action is further discovered in the albumen/SnO2 NWs composite system. The underlying mechanism is interpreted in terms of the fluorescence resonance energy transfer (FRET) from the chicken albumen protein to SnO2 NWs. More importantly, the giant oscillator strength of shallow defect states, which is served orders of magnitude larger than that of the free exciton, plays a decisive role. Our approach therefore shows that bio-materials exhibit a great potential in applications for novel light emitters, which may open up a new avenue for the development of bio-inspired optoelectronic devices.

  10. Nonequilibrium Green's function formulation of intersubband absorption for nonparabolic single-band effective mass Hamiltonian

    SciTech Connect

    Kolek, Andrzej

    2015-05-04

    The formulas are derived that enable calculations of intersubband absorption coefficient within nonequilibrium Green's function method applied to a single-band effective-mass Hamiltonian with the energy dependent effective mass. The derivation provides also the formulas for the virtual valence band components of the two-band Green's functions which can be used for more exact estimation of the density of states and electrons and more reliable treatment of electronic transport in unipolar n-type heterostructure semiconductor devices.

  11. Water ice self-absorption in three Ophiuchus edge-on disks

    NASA Astrophysics Data System (ADS)

    Duchene, Gaspard; Beck, Tracy; Grosso, Nicolas; McCabe, Caer; Menard, Francois; Pinte, Christophe

    2008-02-01

    We propose to use NIRI to measure the depth and shape of the 3(micron) water ice absorption feature in three edge-on disks in the Ophiuchus molecular cloud. This will provide us with an estimate of the total column density of ice in these disks and an indication of the thermal processing it has experienced. In protoplanetary disks, water ice coats dust grains in the majority of the disk volume and plays a major role in favoring grain-grain sticking during collisions, a key phenomenon towards the formation of planetesimals. In edge-on disks, the disk near- infrared thermal radiation, arising from the innermost regions, provides a continuous background that can be absorbed by water ice in the cold outer regions of the disks. These systems therefore offer a unique opportunity to probe water ice in protoplanetary disks. The proposed observations will double the number of edge-on disks with detected water ice absorption and represent the first such observations in the Ophiuchus molecular cloud.

  12. 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.

  13. Fermi level stabilization and band edge energies in Cd{sub x}Zn{sub 1−x}O alloys

    SciTech Connect

    Detert, Douglas M.; Tom, Kyle B.; Dubon, Oscar D.; Battaglia, Corsin; Javey, Ali; Denlinger, Jonathan D.; Lim, Sunnie H. N.; Anders, André; Yu, Kin M.; Walukiewicz, Wladek

    2014-06-21

    We have measured the band edge energies of Cd{sub x}Zn{sub 1−x}O thin films as a function of composition by three independent techniques: we determine the Fermi level stabilization energy by pinning the Fermi level with ion irradiation, measure the binding energy of valence band states and core levels by X-ray photoelectron spectroscopy, and probe shifts in the conduction band and valence band density of states using soft X-ray absorption and emission spectroscopy, respectively. The three techniques find consensus in explaining the origin of compositional trends in the optical-bandgap narrowing upon Cd incorporation in wurtzite ZnO and widening upon Zn incorporation in rocksalt CdO. The conduction band minimum is found to be stationary for both wurtzite and rocksalt alloys, and a significant upward rise of the valence band maximum accounts for the majority of these observed bandgap changes. Given these band alignments, alloy disorder scattering is found to play a negligible role in decreasing the electron mobility for all alloys. These band alignment details, combined with the unique optical and electrical properties of the two phase regimes, make CdZnO alloys attractive candidates for photoelectrochemical water splitting applications.

  14. 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.

  15. Absorption-edge transmission technique using Ce- 139 for measurement of stable iodine concentration.

    PubMed

    Sorenson, J A

    1979-12-01

    We have investigated a technique for measuring stable iodine concentrations by absorption-edge transmission measurements using a Ce 139 radiation source. The lanthanum daughter emits characteristic x-rays whose energies just bracket the absorption edge of iodine at 33.2 keV. Relative transmission of these x-rays is sensitive to iodine concentration in the sample, but is relatively insensitive to other elements. By applying energy-selective beam filtration, it is possible to determine the relative transmission of these closely spaced x-ray energies with NaI(Tl) detectors. Optimizations of sample thickness, detector thickness, and Ce-139 source activity are discussed. Using sample volumes of about 10 ml, one can determine iodine concentration to an uncertainty (standard deviation) of +/- 5 microgram/ml with a 5-mCi source in a measurement time of 400 sec. Potential clinical applications of the in vitro technique are discussed, along with comparative aspects of the Ce-139 technique and other absorption and fluorescence techniques for measuring stable iodine. PMID:536797

  16. 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.

  17. 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.

  18. 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 -}.

  19. Varied absorption peaks of dual-band metamaterial absorber analysis by using reflection theory

    NASA Astrophysics Data System (ADS)

    Xiong, Han; Yu, Yan-Tao; Tang, Ming-Chun; Chen, Shi-Yong; Liu, Dan-Ping; Ou, Xiang; Zeng, Hao

    2016-03-01

    Cross-resonator metamaterial absorbers (MMA) have been widely investigated from microwave to optical frequencies. However, only part of the factors influencing the absorption properties were analyzed in previous works at the same time. In order to completely understand how the spacer thickness, dielectric parameter and incidence angle affect the absorption properties of the dual-band MMA, two sets of simulation were performed. It was found that with increasing incident angles, the low-frequency absorption peak showed a blue shift, while the high-frequency absorption peaks showed a red shift. However, with the increase in spacer thickness, both of the absorption peaks showed a red shift. By using the reflection theory expressions, the physical mechanism of the cross-resonator MMA was well explained. This method provides an effective way to analyze multi-band absorber in technology.

  20. 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.

  1. Near-Edge X-Ray Absorption Fine Structures Revealed in Core Ionization Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakano, M.; Selles, P.; Lablanquie, P.; Hikosaka, Y.; Penent, F.; Shigemasa, E.; Ito, K.; Carniato, S.

    2013-09-01

    Simultaneous core ionization and core excitation have been observed in the C2H2n (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K-2V) core excited states of the K-1 molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude.

  2. Near-edge x-ray absorption fine structures revealed in core ionization photoelectron spectroscopy.

    PubMed

    Nakano, M; Selles, P; Lablanquie, P; Hikosaka, Y; Penent, F; Shigemasa, E; Ito, K; Carniato, S

    2013-09-20

    Simultaneous core ionization and core excitation have been observed in the C(2)H(2n) (n=1, 2, 3) molecular series using synchrotron radiation and a magnetic bottle time-of-flight electron spectrometer. Rich satellite patterns corresponding to (K(-2)V) core excited states of the K(-1) molecular ions have been identified by detecting in coincidence the photoelectron with the two Auger electrons resulting from the double core hole relaxation. A theoretical model is proposed providing absolute photoionization cross sections and revealing clear signatures of direct (monopolar) and conjugate (dipolar near-edge x-ray absorption fine structure) shakeup lines of comparable magnitude. PMID:24093255

  3. An energy and intensity monitor for X-ray absorption near-edge structure measurements

    NASA Astrophysics Data System (ADS)

    de Jonge, Martin D.; Paterson, David; McNulty, Ian; Rau, Christoph; Brandes, Jay A.; Ingall, Ellery

    2010-07-01

    An in-line X-ray beam energy and intensity monitor has been developed for use in focussed X-ray absorption near-edge spectroscopy (XANES) measurements. The monitor uses only the X-ray intensity that would otherwise bypass our zone-plate focussing optic and relies on a measurement of photoemission current. The monitor is inexpensive, easy to align, and provides valuable feedback about the X-ray energy. Operation of the monitor is demonstrated for measurements of phosphorus XANES. The precision of the energy determination is around 0.5 eV.

  4. Double conical crystal x-ray spectrometer for high resolution ultrafast x-ray absorption near-edge spectroscopy of Al K edge

    NASA Astrophysics Data System (ADS)

    Levy, A.; Dorchies, F.; Fourment, C.; Harmand, M.; Hulin, S.; Santos, J. J.; Descamps, D.; Petit, S.; Bouillaud, R.

    2010-06-01

    An x-ray spectrometer devoted to dynamical studies of transient systems using the x-ray absorption fine spectroscopy technique is presented in this article. Using an ultrafast laser-induced x-ray source, this optical device based on a set of two potassium acid phthalate conical crystals allows the extraction of x-ray absorption near-edge spectroscopy structures following the Al absorption K edge. The proposed experimental protocol leads to a measurement of the absorption spectra free from any crystal reflectivity defaults and shot-to-shot x-ray spectral fluctuation. According to the detailed analysis of the experimental results, a spectral resolution of 0.7 eV rms and relative fluctuation lower than 1% rms are achieved, demonstrated to be limited by the statistics of photon counting on the x-ray detector.

  5. Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Sigircik, Gokmen; Erken, Ozge; Tuken, Tunc; Gumus, Cebrail; Ozkendir, Osman M.; Ufuktepe, Yuksel

    2015-06-01

    Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn2+ and OH-) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (Tc) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated Eg values are in the range 3.28-3.41 eV and 3.22-3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm2 V-1 s-1 and 126.2 to 204.7 cm2 V-1 s-1 for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge spectrum is dominated by the transition of Zn 1s core electrons into the unoccupied Zn 4p states of the conduction band. Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valence band electrons is different. Moreover, the density states of Zn 4p are higher for ZnO nanorods.

  6. Solvation effects on the band edge positions of photocatalysts from first principles.

    PubMed

    Ping, Yuan; Sundararaman, Ravishankar; Goddard, William A

    2015-11-11

    The band edge positions of photocatalysts relative to the redox potentials of water play an important role in determining the efficiency of photoelectrochemical cells. These band positions depend on the structure of the solid-liquid interface, but direct ab initio molecular dynamics calculations of these interfaces, while expected to be accurate, are too computationally demanding for high-throughput materials screening. Thus rapid theoretical screening of new photocatalyst materials requires simplified continuum solvation models that are suitable for treating solid-liquid interfaces. In this paper, we evaluate the accuracy of the recently developed CANDLE and SaLSA continuum solvation models for predicting solvation effects on the band positions of several well-studied surfaces [Si(111), TiO2(110), IrO2(110) and WO3(001)] in water. We find that the solvation effects vary considerably, ranging from <0.5 eV for hydrophobic surfaces, 0.5-1 eV for many hydrophilic oxide surfaces, to ∼2 eV for oxygen-deficient surfaces. The solvation model predictions are in excellent agreement (within ∼0.1 eV) with ab initio molecular dynamics results where available, and in good agreement (within ∼0.2-0.3 eV) with experimental measurements. We also predict the energetics for surface oxygen vacancies and their effect on the band positions of the hydrated WO3(001) surface, leading to an explanation for why the solvation shift observed experimentally is substantially larger than predicted for the ideal surface. Based on the correlation between solvation shift and the type of surface and solvent, we suggest approaches to engineer the band positions of surfaces in aqueous and non-aqueous solutions. PMID:26513300

  7. Comparing Broad-Band and Red Edge-Based Spectral Vegetation Indices to Estimate Nitrogen Concentration of Crops Using Casi Data

    NASA Astrophysics Data System (ADS)

    Wang, Yanjie; Liao, Qinhong; Yang, Guijun; Feng, Haikuan; Yang, Xiaodong; Yue, Jibo

    2016-06-01

    In recent decades, many spectral vegetation indices (SVIs) have been proposed to estimate the leaf nitrogen concentration (LNC) of crops. However, most of these indices were based on the field hyperspectral reflectance. To test whether they can be used in aerial remote platform effectively, in this work a comparison of the sensitivity between several broad-band and red edge-based SVIs to LNC is investigated over different crop types. By using data from experimental LNC values over 4 different crop types and image data acquired using the Compact Airborne Spectrographic Imager (CASI) sensor, the extensive dataset allowed us to evaluate broad-band and red edge-based SVIs. The result indicated that NDVI performed the best among the selected SVIs while red edge-based SVIs didn't show the potential for estimating the LNC based on the CASI data due to the spectral resolution. In order to search for the optimal SVIs, the band combination algorithm has been used in this work. The best linear correlation against the experimental LNC dataset was obtained by combining the 626.20nm and 569.00nm wavebands. These wavelengths correspond to the maximal chlorophyll absorption and reflection position region, respectively, and are known to be sensitive to the physiological status of the plant. Then this linear relationship was applied to the CASI image for generating an LNC map, which can guide farmers in the accurate application of their N fertilization strategies.

  8. 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.

  9. Millimeter Wave Absorption Bands of Silver/copper Iodides-Phosphate Glasses

    NASA Astrophysics Data System (ADS)

    Awano, Teruyoshi; Takahashi, Toshiharu

    2013-07-01

    Millimeter wave absorption spectra of silver halides doped silver phosphate glasses were measured using an intense coherent transition radiation. Two bands were observed at 8.4cm-1 and 6.3cm-1 in AgI doped AgPO3 glass and 8.7cm-1 and 6.1cm-1 in AgBr doped one. Small difference of peak positions between these glasses suggests that these absorption bands are concerned with a large number of silver ions in dopant molecules. Cu+ conducting glasses

  10. The northern edge of the band of solar wind variability: Ulysses at {approximately}4.5AU

    SciTech Connect

    Gosling, J.T.; Bame, S.J.; Feldman, W.C.; McComas, D.J.; Riley, P.; Goldstein, B.E.; Neugebauer, M.

    1997-02-01

    Ulysses observations reveal that the northern edge of the low-latitude band of solar wind variability at {approximately}4.5AU was located at N30{degree} in the latter part of 1996 when solar activity was at a minimum. This edge latitude is intermediate between edge latitudes found during previous encounters with the band edge along different portions of Ulysses{close_quote} polar orbit about the Sun. Corotating interaction regions, CIRs, near the northern edge of the band were tilted in such a manner that the forward and reverse shocks bounding the CIRs were propagating equatorward and poleward, respectively, providing definite confirmation that CIRs have opposed tilts in the opposite solar hemispheres. No shocks or coronal mass ejections, CMEs, were detected during the {approximately}1.5y traverse of the northern, high-latitude northern hemisphere; however, at the northern edge of the band of variability an expanding CME was observed that was driving a shock into the high-speed wind.{copyright} 1997 American Geophysical Union

  11. Phase transition-induced band edge engineering of BiVO4 to split pure water under visible light

    PubMed Central

    Jo, Won Jun; Kang, Hyun Joon; Kong, Ki-Jeong; Lee, Yun Seog; Park, Hunmin; Lee, Younghye; Buonassisi, Tonio; Gleason, Karen K.; Lee, Jae Sung

    2015-01-01

    Through phase transition-induced band edge engineering by dual doping with In and Mo, a new greenish BiVO4 (Bi1-XInXV1-XMoXO4) is developed that has a larger band gap energy than the usual yellow scheelite monoclinic BiVO4 as well as a higher (more negative) conduction band than H+/H2 potential [0 VRHE (reversible hydrogen electrode) at pH 7]. Hence, it can extract H2 from pure water by visible light-driven overall water splitting without using any sacrificial reagents. The density functional theory calculation indicates that In3+/Mo6+ dual doping triggers partial phase transformation from pure monoclinic BiVO4 to a mixture of monoclinic BiVO4 and tetragonal BiVO4, which sequentially leads to unit cell volume growth, compressive lattice strain increase, conduction band edge uplift, and band gap widening. PMID:26508636

  12. Impact ionization across the conduction-band-edge discontinuity of quantum-well heterostructures

    NASA Technical Reports Server (NTRS)

    Chuang, S. L.; Hess, K.

    1986-01-01

    Impact ionization across the band-edge discontinuity of quantum-well heterostructures is studied theoretically. A heterolayer structure of alternating Al(x)Ga(1-x)As and GaAs layers is considered where the GaAs layers are heavily doped with donors. Thus a large number of electrons is confined to the quantum-well region. Incident electrons are heated up by applied electric fields and collide with the electrons confined in the well regions. Both the ionization rate as a function of the incident energy, and average ionization rates are computed. Device applications of such multiple quantum-well structures and the possibility of a complete analog to the conventional photomultiplier are discussed.

  13. POLYCYCLIC AROMATIC HYDROCARBONS WITH ARMCHAIR EDGES AND THE 12.7 μm BAND

    SciTech Connect

    Candian, A.; Tielens, A. G. G. M.; Sarre, P. J.

    2014-08-10

    In this Letter, we report the results of density functional theory calculations on medium-sized neutral polycyclic aromatic hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common, although generally weak. Therefore, we propose that armchair PAHs with N{sub C} > 65 are responsible for the 12.7 μm aromatic infrared band in H II regions and discuss the astrophysical implications in the context of the PAH life cycle.

  14. Giant amplification in degenerate band edge slow-wave structures interacting with an electron beam

    NASA Astrophysics Data System (ADS)

    Othman, Mohamed A. K.; Veysi, Mehdi; Figotin, Alexander; Capolino, Filippo

    2016-03-01

    We propose a new amplification regime based on a synchronous operation of four degenerate electromagnetic (EM) modes in a slow-wave structure and the electron beam, referred to as super synchronization. These four EM modes arise in a Fabry-Pérot cavity when degenerate band edge (DBE) condition is satisfied. The modes interact constructively with the electron beam resulting in superior amplification. In particular, much larger gains are achieved for smaller beam currents compared to conventional structures based on synchronization with only a single EM mode. We demonstrate giant gain scaling with respect to the length of the slow-wave structure compared to conventional Pierce type single mode traveling wave tube amplifiers. We construct a coupled transmission line model for a loaded waveguide slow-wave structure exhibiting a DBE, and investigate the phenomenon of giant gain via super synchronization using the Pierce model generalized to multimode interaction.

  15. Polycyclic Aromatic Hydrocarbons with Armchair Edges and the 12.7 μm Band

    NASA Astrophysics Data System (ADS)

    Candian, A.; Sarre, P. J.; Tielens, A. G. G. M.

    2014-08-01

    In this Letter, we report the results of density functional theory calculations on medium-sized neutral polycyclic aromatic hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common, although generally weak. Therefore, we propose that armchair PAHs with NC > 65 are responsible for the 12.7 μm aromatic infrared band in H II regions and discuss the astrophysical implications in the context of the PAH life cycle.

  16. Disorder-free localization around the conduction band edge of crossing and kinked silicon nanowires

    SciTech Connect

    Keleş, Ümit; Çakan, Aslı; Bulutay, Ceyhun

    2015-02-14

    We explore ballistic regime quantum transport characteristics of oxide-embedded crossing and kinked silicon nanowires (NWs) within a large-scale empirical pseudopotential electronic structure framework, coupled to the Kubo-Greenwood transport analysis. A real-space wave function study is undertaken and the outcomes are interpreted together with the findings of ballistic transport calculations. This reveals that ballistic transport edge lies tens to hundreds of millielectron volts above the lowest unoccupied molecular orbital, with a substantial number of localized states appearing in between, as well as above the former. We show that these localized states are not due to the oxide interface, but rather core silicon-derived. They manifest the wave nature of electrons brought to foreground by the reflections originating from NW junctions and bends. Hence, we show that the crossings and kinks of even ultraclean Si NWs possess a conduction band tail without a recourse to atomistic disorder.

  17. High degree of polarization of the near-band-edge photoluminescence in ZnO nanowires

    PubMed Central

    2011-01-01

    We investigated the polarization dependence of the near-band-edge photoluminescence in ZnO strain-free nanowires grown by vapor phase technique. The emission is polarized perpendicular to the nanowire axis with a large polarization ratio (as high as 0.84 at 4.2 K and 0.63 at 300 K). The observed polarization ratio is explained in terms of selection rules for excitonic transitions derived from the k·p theory for ZnO. The temperature dependence of the polarization ratio evidences a gradual activation of the XC excitonic transition. PACS: 78.55.Cr, 77.22.Ej, 81.07.Gf. PMID:21854578

  18. The study of optical band edge property of bismuth oxide nanowires α-Bi2O3.

    PubMed

    Ho, Ching-Hwa; Chan, Ching-Hsiang; Huang, Ying-Sheng; Tien, Li-Chia; Chao, Liang-Chiun

    2013-05-20

    The α-phase Bi(2)O(3) (α-Bi(2)O(3)) is a crucial and potential visiblelight photocatalyst material needless of intentional doping on accommodating band gap. The understanding on fundamental optical property of α-Bi(2)O(3) is important for its extended applications. In this study, bismuth oxide nanowires with diameters from tens to hundreds nm have been grown by vapor transport method driven with vapor-liquid-solid mechanism on Si substrate. High-resolution transmission electron microscopy and Raman measurement confirm α phase of monoclinic structure for the as-grown nanowires. The axial direction for the as-grown nanowires was along < 122 >. The band-edge structure of α-Bi(2)O(3) has been probed experimentally by thermoreflectance (TR) spectroscopy. The direct band gap was determined accurately to be 2.91 eV at 300 K. Temperaturedependent TR measurements of 30-300 K were carried out to evaluate temperature-energy shift and line-width broadening effect for the band edge of α-Bi(2)O(3) thin-film nanowires. Photoluminescence (PL) experiments at 30 and 300 K were carried out to identify band-edge emission as well as defect luminescence for the α-Bi(2)O(3) nanowires. On the basis of experimental analyses of TR and PL, optical characteristics of direct band edge of α-Bi(2)O(3) nanowires have thus been realized. PMID:23736418

  19. Broadening of absorption band by coupled gap plasmon resonances in a near-infrared metamaterial absorber

    NASA Astrophysics Data System (ADS)

    Cong, Jiawei; Yao, Hongbing; Gong, Daolei; Chen, Mingyang; Tong, Yanqun; Fu, Yonghong; Ren, Naifei

    2016-07-01

    We propose a strategy to broaden the absorption band of the conventional metamaterial absorber by incorporating alternating metal/dielectric films. Up to 7-fold increase in bandwidth and ∼95% average absorption are achieved arising from the coupling of induced multiple gap plasmon resonances. The resonance coupling is analytically demonstrated using the coupled oscillator model, which reveals that both the optimal coupling strength and the resonance wavelength matching are required for the enhancement of absorption bandwidth. The presented multilayer design is easily fabricated and readily implanted to other absorber configurations, offering a practical avenue for applications in photovoltaic cells and thermal emitters.

  20. High sensitivity ultra-broad-band absorption spectroscopy of inductively coupled chlorine plasma

    NASA Astrophysics Data System (ADS)

    Marinov, Daniil; Foucher, Mickaël; Campbell, Ewen; Brouard, Mark; Chabert, Pascal; Booth, Jean-Paul

    2016-06-01

    We propose a method to measure the densities of vibrationally excited Cl2(v) molecules in levels up to v  =  3 in pure chlorine inductively coupled plasmas (ICPs). The absorption continuum of Cl2 in the 250–450 nm spectral range is deconvoluted into the individual components originating from the different vibrational levels of the ground state, using a set of ab initio absorption cross sections. It is shown that gas heating at constant pressure is the major depletion mechanism of the Cl2 feedstock in the plasma. In these line-integrated absorption measurements, the absorption by the hot (and therefore rarefied) Cl2 gas in the reactor centre is masked by the cooler (and therefore denser) Cl2 near the walls. These radial gradients in temperature and density make it difficult to assess the degree of vibrational excitation in the centre of the reactor. The observed line-averaged vibrational distributions, when analyzed taking into account the radial temperature gradient, suggest that vibrational and translational degrees of freedom in the plasma are close to local equilibrium. This can be explained by efficient vibrational-translational (VT) relaxation between Cl2 and Cl atoms. Besides the Cl2(v) absorption band, a weak continuum absorption is observed at shorter wavelengths, and is attributed to photodetachment of Cl‑ negative ions. Thus, line-integrated densities of negative ions in chlorine plasmas can be directly measured using broad-band absorption spectroscopy.

  1. Diversity in the Visible-NIR Absorption Band Characteristics of Lunar and Asteroidal Plagioclase

    NASA Technical Reports Server (NTRS)

    Hiroi, T.; Kaiden, H.; Misawa, K.; Kojima, H.; Uemoto, K.; Ohtake, M.; Arai, T.; Sasaki, S.; Takeda, H.; Nyquist, L. E.; Shih, C.-Y.

    2012-01-01

    Studying the visible and near-infrared (VNIR) spectral properties of plagioclase has been challenging because of the difficulty in obtaining good plagioclase separates from pristine planetary materials such as meteorites and returned lunar samples. After an early study indicated that the 1.25 m band position of plagioclase spectrum might be correlated with the molar percentage of anorthite (An#) [1], there have been few studies which dealt with the band center behavior. In this study, the VNIR absorption band parameters of plagioclase samples have been derived using the modified Gaussian model (MGM) [2] following a pioneering study by [3].

  2. Correlating structure and electronic band-edge properties in organolead halide perovskites nanoparticles.

    PubMed

    Zhu, Qiushi; Zheng, Kaibo; Abdellah, Mohamed; Generalov, Alexander; Haase, Dörthe; Carlson, Stefan; Niu, Yuran; Heimdal, Jimmy; Engdahl, Anders; Messing, Maria E; Pullerits, Tonu; Canton, Sophie E

    2016-06-01

    After having emerged as primary contenders in the race for highly efficient optoelectronics materials, organolead halide perovskites (OHLP) are now being investigated in the nanoscale regime as promising building blocks with unique properties. For example, unlike their bulk counterpart, quantum dots of OHLP are brightly luminescent, owing to large exciton binding energies that cannot be rationalized solely on the basis of quantum confinement. Here, we establish the direct correlation between the structure and the electronic band-edge properties of CH3NH3PbBr3 nanoparticles. Complementary structural and spectroscopic measurements probing long-range and local order reveal that lattice strain influences the nature of the valence band and modifies the subtle stereochemical activity of the Pb(2+) lone-pair. More generally, this work demonstrates that the stereochemical activity of the lone-pair at the metal site is a specific physicochemical parameter coupled to composition, size and strain, which can be employed to engineer novel functionalities in OHLP nanomaterials. PMID:27189431

  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. 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

  5. Evaluation of Sentinel-2 Red-Edge Bands for Empirical Estimation of Green LAI and Chlorophyll Content

    PubMed Central

    Delegido, Jesús; Verrelst, Jochem; Alonso, Luis; Moreno, José

    2011-01-01

    ESA’s upcoming satellite Sentinel-2 will provide Earth images of high spatial, spectral and temporal resolution and aims to ensure continuity for Landsat and SPOT observations. In comparison to the latter sensors, Sentinel-2 incorporates three new spectral bands in the red-edge region, which are centered at 705, 740 and 783 nm. This study addresses the importance of these new bands for the retrieval and monitoring of two important biophysical parameters: green leaf area index (LAI) and chlorophyll content (Ch). With data from several ESA field campaigns over agricultural sites (SPARC, AgriSAR, CEFLES2) we have evaluated the efficacy of two empirical methods that specifically make use of the new Sentinel-2 bands. First, it was shown that LAI can be derived from a generic normalized difference index (NDI) using hyperspectral data, with 674 nm with 712 nm as best performing bands. These bands are positioned closely to the Sentinel-2 B4 (665 nm) and the new red-edge B5 (705 nm) band. The method has been applied to simulated Sentinel-2 data. The resulting green LAI map was validated against field data of various crop types, thereby spanning a LAI between 0 and 6, and yielded a RMSE of 0.6. Second, the recently developed “Normalized Area Over reflectance Curve” (NAOC), an index that derives Ch from hyperspectral data, was studied on its compatibility with simulated Sentinel-2 data. This index integrates the reflectance curve between 643 and 795 nm, thereby including the new Sentinel-2 bands in the red-edge region. We found that these new bands significantly improve the accuracy of Ch estimation. Both methods emphasize the importance of red-edge bands for operational estimation of biophysical parameters from Sentinel-2. PMID:22164004

  6. Evaluation of Sentinel-2 red-edge bands for empirical estimation of green LAI and chlorophyll content.

    PubMed

    Delegido, Jesús; Verrelst, Jochem; Alonso, Luis; Moreno, José

    2011-01-01

    ESA's upcoming satellite Sentinel-2 will provide Earth images of high spatial, spectral and temporal resolution and aims to ensure continuity for Landsat and SPOT observations. In comparison to the latter sensors, Sentinel-2 incorporates three new spectral bands in the red-edge region, which are centered at 705, 740 and 783 nm. This study addresses the importance of these new bands for the retrieval and monitoring of two important biophysical parameters: green leaf area index (LAI) and chlorophyll content (Ch). With data from several ESA field campaigns over agricultural sites (SPARC, AgriSAR, CEFLES2) we have evaluated the efficacy of two empirical methods that specifically make use of the new Sentinel-2 bands. First, it was shown that LAI can be derived from a generic normalized difference index (NDI) using hyperspectral data, with 674 nm with 712 nm as best performing bands. These bands are positioned closely to the Sentinel-2 B4 (665 nm) and the new red-edge B5 (705 nm) band. The method has been applied to simulated Sentinel-2 data. The resulting green LAI map was validated against field data of various crop types, thereby spanning a LAI between 0 and 6, and yielded a RMSE of 0.6. Second, the recently developed "Normalized Area Over reflectance Curve" (NAOC), an index that derives Ch from hyperspectral data, was studied on its compatibility with simulated Sentinel-2 data. This index integrates the reflectance curve between 643 and 795 nm, thereby including the new Sentinel-2 bands in the red-edge region. We found that these new bands significantly improve the accuracy of Ch estimation. Both methods emphasize the importance of red-edge bands for operational estimation of biophysical parameters from Sentinel-2. PMID:22164004

  7. 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

  8. 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. PMID:18728323

  9. Attenuation studies near K-absorption edges using Compton scattered 241 Am gamma rays

    NASA Astrophysics Data System (ADS)

    Abdullah, K. K.; Ramachandran, N.; Karunakaran Nair, K.; Babu, B. R. S.; Joseph, Antony; Thomas, Rajive; Varier, K. M.

    2008-04-01

    We have carried out photon attenuation measurements at several energies in the range from 49.38 keV to 57.96 keV around the K-absorption edges of the rare earth elements Sm, Eu, Gd, Tb, Dy and Er using 59.54 keV gamma rays from ^{241}Am source after Compton scattering from an aluminium target. Pellets of oxides of the rare earth elements were chosen as mixture absorbers in these investigations. A narrow beam good geometry set-up was used for the attenuation measurements. The scattered gamma rays were detected by an HPGe detector. The results are consistent with theoretical values derived from the XCOM package.

  10. Role of exciton-phonon interactions and disordering processes in the formation of the absorption edge in Cu6P(S1- x Sex)5Br crystals

    NASA Astrophysics Data System (ADS)

    Studenyak, I. P.; Kranjcec, M.; Suslikov, L. M.; Kovacs, D. Sh.; Pan'ko, V. V.

    2002-04-01

    The absorption edge in Cu6P(S1- x Sex)5Br crystals has been studied for strong absorption in the temperature range of 77 330 K. The parameters of the Urbach absorption edge and exciton-phonon interactions in Cu6P(S1- x Sex)5Br crystals are determined and their effect on the composition disorder is studied.

  11. Laboratory Measurements of the 940, 1130, and 1370 nm Water Vapor Absorption Band Profiles

    NASA Technical Reports Server (NTRS)

    Giver, Lawrence P.; Gore, Warren J.; Pilewskie, P.; Freedman, R. S.; Chackerian, C., Jr.; Varanasi, P.

    2001-01-01

    We have used the solar spectral flux radiometer (SSFR) flight instrument with the Ames 25 meter base-path White cell to obtain about 20 moderate resolution (8 nm) pure water vapor spectra from 650 to 1650 nm, with absorbing paths from 806 to 1506 meters and pressures up to 14 torr. We also obtained a set at 806 meters with several different air-broadening pressures. Model simulations were made for the 940, 1130, and 1370 nm absorption bands for some of these laboratory conditions using the Rothman, et al HITRAN-2000 linelist. This new compilation of HITRAN includes new intensity measurements for the 940 nm region. We compared simulations for our spectra of this band using HITRAN-2000 with simulations using the prior HITRAN-1996. The simulations of the 1130 nm band show about 10% less absorption than we measured. There is some evidence that the total intensity of this band is about 38% stronger than the sum of the HITRAN line intensities in this region. In our laboratory conditions the absorption depends approximately on the square root of the intensity. Thus, our measurements agree that the band is stronger than tabulated in HITRAN, but by about 20%, substantially less than the published value. Significant differences have been shown between Doppler-limited resolution spectra of the 1370 nm band obtained at the Pacific Northwest National Laboratory and HITRAN simulations. Additional new intensity measurements in this region are continuing to be made. We expect the simulations of our SSFR lab data of this band will show the relative importance of improving the HITRAN line intensities of this band for atmospheric measurements.

  12. Isothermal annealing of a 620 nm optical absorption band in Brazilian topaz crystals

    NASA Astrophysics Data System (ADS)

    Isotani, Sadao; Matsuoka, Masao; Albuquerque, Antonio Roberto Pereira Leite

    2013-04-01

    Isothermal decay behaviors, observed at 515, 523, 562, and 693 K, for an optical absorption band at 620 nm in gamma-irradiated Brazilian blue topaz were analyzed using a kinetic model consisting of O- bound small polarons adjacent to recombination centers (electron traps). The kinetic equations obtained on the basis of this model were solved using the method of Runge-Kutta and the fit parameters describing these defects were determined with a grid optimization method. Two activation energies of 0.52±0.08 and 0.88±0.13 eV, corresponding to two different structural configurations of the O- polarons, explained well the isothermal decay curves using first-order kinetics expected from the kinetic model. On the other hand, thermoluminescence (TL) emission spectra measured at various temperatures showed a single band at 400 nm in the temperature range of 373-553 K in which the 620 nm optical absorption band decreased in intensity. Monochromatic TL glow curve data at 400 nm extracted from the TL emission spectra observed were found to be explained reasonably by using the knowledge obtained from the isothermal decay analysis. This suggests that two different structural configurations of O- polarons are responsible for the 620 nm optical absorption band and that the thermal annealing of the polarons causes the 400 nm TL emission band.

  13. Band-integrated infrared absorptance of low-molecular-weight paraffin hydrocarbons at high temperatures.

    PubMed

    Fuss, S P; Hall, M J; Ezekoye, O A

    1999-05-01

    The spectral absorptance of the 3.4-microm band of methane, ethane, propane, and butane has been measured with a Fourier transform infrared spectrometer over a range of temperatures from 296 to 900 K. The measurements were made at a 4-cm(-1) resolution and integrated over the entire band to give the total absorptance. The total absorptance is found to behave in such a way that it can be correlated by a combination of algebraic expressions that depend on the gas temperature and concentration. Average discrepancies between the correlations and the measurements are less than 4%, with maximum differences of no greater than 17%. In addition, the correlations presented here for methane are shown to be in good agreement with established models. Expressions given for the integrated intensity of each gas show an inverse dependence on temperature, reflecting the associated change in density. PMID:18319871

  14. Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory

    SciTech Connect

    George, S.DeBeer; Petrenko, T.; Neese, F.

    2009-05-14

    Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O{sub h} to T{sub d} geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis set on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.

  15. Time-Dependent Density Functional Calculations of Ligand K-Edge X-Ray Absorption Spectra

    SciTech Connect

    DeBeer George, S.; Petrenko, T.; Neese, F.

    2007-07-10

    X-ray absorption spectra (XAS) at the Cl and S K edge and Mo L edge have been calculated at the TDDFT level for a series of dioxomolybdenum complexes LMoO{sub 2}X (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, X = Cl, SCH{sub 2}Ph, OPh), which play an important role in modeling the catalytic cycle of the sulfite oxidase enzyme. Also, the XAS spectra of model molecules of the Mo complexes have been simulated and interpreted in terms of the Mo 4d orbital splitting, in order to find possible correlations with the spectral pattern of the complexes. Comparison with the available experimental data allows us to assess the performances of the present computational scheme to describe the core excitations in large bioinorganic systems. The theoretical interpretation of the spectral features of both the metal and ligand core excitations in terms of the oscillator strength distribution provides important insight into the covalency of the metal-ligand bond.

  16. Effect of Sn on the optical band gap determined using absorption spectrum fitting method

    SciTech Connect

    Heera, Pawan; Kumar, Anup; Sharma, Raman

    2015-05-15

    We report the preparation and the optical studies on tellurium rich glasses thin films. The thin films of Se{sub 30}Te{sub 70-x} Sn{sub x} system for x= 0, 1.5, 2.5 and 4.5 glassy alloys prepared by melt quenching technique are deposited on the glass substrate using vacuum thermal evaporation technique. The analysis of absorption spectra in the spectral range 400nm–4000 nm at room temperature obtained from UV-VIS-NIR spectrophotometer [Perkin Elmer Lamda-750] helps us in the optical characterization of the thin films under study. The absorption spectrum fitting method is applied by using the Tauc’s model for estimating the optical band gap and the width of the band tail of the thin films. The optical band gap is calculated and is found to decrease with the Sn content.

  17. 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.

  18. Failure of Energy Transfer between Identical Aromatic Molecules on Excitation at the Long Wave Edge of the Absorption Spectrum

    PubMed Central

    Weber, Gregorio; Shinitzky, Meir

    1970-01-01

    Electronic energy transfer among identical molecules has been followed by the depolarization of the fluorescence in concentrated solutions as well as in dimers, polymers, and micelle systems. In the many aromatic fluorophores examined, unlike a few nonaromatic ones, transfer is much decreased or altogether undetectable on excitation at the red edge of the absorption spectrum. The phenomenon is not due to the transfer taking place during a small fraction of the total fluorescence lifetime, nor is it explainable by a decrease in overlap of absorption and emission upon edge excitation. PMID:16591825

  19. The effect of nanocrystallite size in monoclinic HfO{sub 2} films on lattice expansion and near-edge optical absorption

    SciTech Connect

    Cisneros-Morales, M. C.; Aita, C. R.

    2010-05-10

    Nanocrystalline monoclinic HfO{sub 2} films were sputter deposited on fused silica substrates, air annealed at 573 to 1273 K to affect crystallite growth, and analyzed by x-ray diffraction and spectrophotometry. Lattice expansion occurs with diminishing crystallite size. O 2p->Hf 5d interband absorption dominates the optical edge at energy E>=6.24 eV, with an optical band gap, E{sub o}=5.48+-0.023, which is independent of crystallite size. However, the strength of a localized resonant band, with onset at 5.65 eV and maximum at 5.94 eV, is affected by crystallite size. Its polaronic origin in a perfect HfO{sub 2} lattice is discussed.

  20. First-principles study of phonon effects in x-ray absorption near-edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Nemausat, R.; Brouder, Ch; Gervais, Ch; Cabaret, D.

    2016-05-01

    Usually first-principles x-ray absorption near-edge structure (XANES) calculations are performed in the Born-Oppenheimer approximation assuming a static lattice, whereas the nuclear motion undoubtedly impacts XANES spectra notably at the K pre-edge of light elements in oxides. Here, an efficient method based on density-functional theory to account for quantum thermal fluctuations of nuclei is developed and is successfully applied to the K edge of corundum for temperatures up to 930 K. The zero-point motion influence is estimated. Comparison is made with previous theoretical approaches also developed to account for vibrations in XANES.

  1. Radiation absorption by the C2 band systems for Jupiter entry conditions

    NASA Technical Reports Server (NTRS)

    Sutton, K.; Moss, J. N.

    1979-01-01

    Revised values of the absorption cross sections for seven electronic band systems of C2 have been calculated using recently published experimental data for the electronic transition moments. Using these revised C2 cross section values, computations were made for the radiating flow field over a Jupiter entry probe with coupled ablation injection from a carbon-phenolic heat shield. Results are presented which show that radiation absorption within the ablation layer for the spectral range of 4 to 6 eV is less than that predicted using previous C2 absorption cross section values. The effect of the reduced radiation absorption by the C2 molecule is an increase in the radiative heating rates and ablation mass loss rates for the Jupiter entry conditions considered in the study.

  2. Temperature and high-pressure dependent x-ray absorption of SmNiO3 at the Ni K and Sm L3 edges

    NASA Astrophysics Data System (ADS)

    Massa, Néstor E.; Ramos, Aline Y.; Tolentino, Helio C. N.; Sousa-Neto, Narcizo M.; Fonseca, Jairo, Jr.; Alonso, José Antonio

    2015-12-01

    We report on x-ray absorption near-edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements of SmNiO3 from 20 K to 600 K and up to 38 GPa at the Ni K and Sm L3 edges. A multiple component pre-Ni K edge tail is understood, originating from 1 s transitions to 3d-4p states while a post-edge shoulder increases distinctively smoothly, at about the insulator to metal phase transition (TIM), due to the reduction of electron-phonon interactions as the Ni 3d and O 2p band overlap triggers the metallic phase. This effect is concomitant with pressure-induced Ni-O-Ni angle increments toward more symmetric Ni3+ octahedra of the rhombohedral R¯3c space group. Room temperature pressure-dependent Ni white line peak energies have an abrupt ˜3.10 ± 0.04 GPa valence discontinuity from non-equivalent Ni3+δ + Ni3-δ charge disproportionate net unresolved absorber turning at ˜TIM into Ni3+ of the orthorhombic Pbnm metal oxide phase. At 20 K the overall white line response, still distinctive at TIM ˜8.1 ± 0.6 GPa is much smoother due to localization. Octahedral bond contraction up to 38 GPa and at 300 K and 20 K show breaks in its monotonic increase at the different structural changes. The Sm L3 edge does not show distinctive behaviors either at 300 K or 20 K up to about 35 GPa but the perovskite Sm cage, coordinated to eight oxygen atoms, undergoes strong uneven bond contractions at intermediate pressures where we found the coexistence of octahedral and rhombohedral superexchange angle distortions. We found that the white line pressure-dependent anomaly may be used as an accurate alternative for delineating pressure-temperature phase diagrams.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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.

  4. Absorption spectrum of NO in the {gamma}(O, O) band

    SciTech Connect

    Zobnin, A.V.; Korotkov, A.N.

    1995-05-01

    A promising technique for determining the concentration of nitrogen oxide in the air of an industrial zone and in process gases is the measurement of the absorption of UV radiation by this molecule in the {gamma}(O,O) band with the center of {lambda}{sub 0} = 226.5 nm. This band corresponds to the transition X{sup 2}{Pi}{yields}{Alpha}{sup 2}{Sigma} of the NO molecule and is characterized by a complex rotational structure consisting of about 400 lines. This structure cannot be resolved completely by most spectral instruments. However, if the width of the spread function of the device is perceptibly smaller than the width of the given absorption band ({approx_equal}2 nm), but larger than the characteristic space between rotational lines ({approx_equal}0.02 nm), then the recorded transmission spectra of NO are almost insensitive to a change in the form of this function. In the given case, to describe the transmission spectrum it is possible to use the absorption coefficient averaged over rotational lines. And even though the Bouger-Lambert-Beer law is not strictly applicable for this spectrum, the dependence of the transmission spectrum of NO on the optical thickness, temperature, and pressure of the broadening gas can be represented in the form of an empirical dependence that can be useful in practice, for example, when processing the absorption spectra recorded by dispersion gas analyzers. Thus, the need for complex and laborious calculations is avoided, and this simplifies considerably the instrumental implementation of this method of measuring the concentration of NO. The object of the present work is to determine the empirical dependence of the absorption spectrum of NO in the {gamma}(O, O) band on the optical thickness, temperature, and pressure of the broadening gas in the ranges most frequently encountered in operation of dispersion gas analyzers.

  5. Novel Cross-Band Relative Absorption (CoBRA) technique For Measuring Atmospheric Species

    NASA Astrophysics Data System (ADS)

    Prasad, N. S.; Pliutau, D.

    2013-12-01

    We describe a methodology called Cross-Band Relative Absorption (CoBRA) we have implemented to significantly reduce interferences due to variations in atmospheric temperature and pressure in molecular mixing ration measurements [1-4]. The interference reduction is achieved through automatic compensation based on selecting spectral line pairs exhibiting similar evolution behavior under varying atmospheric conditions. The method is applicable to a wide range of molecules including CO2 and CH4 which can be matched with O2 or any other well-mixed atmospheric molecule. Such matching results in automatic simultaneous adjustments of the spectral line shapes at all times with a high precision under varying atmospheric conditions of temperature and pressure. We present the results of our selected CoBRA analysis based on line-by-line calculations and the Modern Era Retrospective Analysis for Research and Applications (MERRA) dataset including more recent evaluation of the error contributions due to water vapor interference effects. References: 1) N. S. Prasad, D. Pliutau, 'Cross-band relative absorption technique for the measurement of molecular mixing ratios.', Optics Express, Vol. 21, Issue 11, pp. 13279-13292 (2013) 2) D. Pliutau and N. S. Prasad, "Cross-band Relative Absorption Technique for Molecular Mixing Ratio Determination," in CLEO: 2013, OSA Technical Digest (online) (Optical Society of America, 2013), paper CW3L.4. 3) Denis Pliutau; Narasimha S. Prasad; 'Semi-empirical validation of the cross-band relative absorption technique for the measurement of molecular mixing ratios',.Proc. SPIE 8731, Laser Radar Technology and Applications XVIII, 87310L (May 20, 2013); doi:10.1117/12.2016661. 4) Denis Pliutau,; Narasimha S. Prasad; 'Comparative analysis of alternative spectral bands of CO2 and O2 for the sensing of CO2 mixing ratios' Proc. SPIE 8718, Advanced Environmental, Chemical, and Biological Sensing Technologies X, 87180L (May 31, 2013); doi:10.1117/12.2016337.

  6. Assignment and rotational analysis of new absorption bands of carbon dioxide isotopologues in Venus spectra

    NASA Astrophysics Data System (ADS)

    Robert, S.; Borkov, Yu. G.; Vander Auwera, J.; Drummond, R.; Mahieux, A.; Wilquet, V.; Vandaele, A. C.; Perevalov, V. I.; Tashkun, S. A.; Bertaux, J. L.

    2013-01-01

    We present absorption bands of carbon dioxide isotopologues, detected by the Solar Occultation for the Infrared Range (SOIR) instrument on board the Venus Express Satellite. The SOIR instrument combines an echelle spectrometer and an Acousto-Optical Tunable Filter (AOTF) for order selection. It performs solar occultation measurements in the Venus atmosphere in the IR region (2.2-4.3 μm), at a resolution of 0.12-0.18 cm-1. The wavelength range probed by SOIR allows a detailed chemical inventory of the Venus atmosphere above the cloud layer (65-150 km) to be made with emphasis on the vertical distributions of gases. Thanks to the SOIR spectral resolution, a new CO2 absorption band was identified: the 21101-01101 band of 16O12C18O with R branch up to J=31. Two other previously reported bands were observed dispelling any doubts about their identifications: the 20001-00001 band of 16O13C18O [Villanueva G, et al. J Quant Spectrosc Radiat Transfer 2008;109:883-894] and the 01111-00001 band of 16O12C18O [Villanueva G, et al. J Quant Spectrosc Radiat Transfer 2008;109:883-894 and Wilquet V, et al. J Quant Spectrosc Radiat Transfer 2008;109:895-905]. These bands were analyzed, and spectroscopic constants characterizing them were obtained. The rotational assignment of the 20001-00001 band was corrected. The present measurements are compared with data available in the HITRAN database.

  7. Thin-walled boron nitride microtubes exhibiting intense band-edge UV emission at room temperature.

    PubMed

    Huang, Yang; Bando, Yoshio; Tang, Chengchun; Zhi, Chunyi; Terao, Takeshi; Dierre, Benjamin; Sekiguchi, Takashi; Golberg, Dmitri

    2009-02-25

    Boron nitride (BN) microtubes were synthesized in a vertical induction furnace using Li(2)CO(3) and B reactants. Their structures and morphologies were investigated using x-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive x-ray spectroscopy. The microtubes have diameters of 1-3 microm, lengths of up to hundreds of micrometers, and well-structured ultrathin walls only approximately 50 nm thick. A mechanism combining the vapor-liquid-solid (VLS) and template self-sacrificing processes is proposed to explain the formation of these novel one-dimensional microstructures, in which the Li(2)O-B(2)O(3) eutectic reaction plays an important role. Cathodoluminescence studies show that even at room temperature the thin-walled BN microtubes can possess an intense band-edge emission at approximately 216.5 nm, which is distinct compared with other BN nanostructures. The study suggests that the thin-walled BN microtubes should be promising for constructing compact deep UV devices and find potential applications in microreactors and microfluidic and drug delivery systems. PMID:19417466

  8. Rotational Profiles of Molecular Absorption Bands in Astrophysically Relevant Conditions: Ab-Initio Approach

    SciTech Connect

    Malloci, Giuliano; Mulas, Giacomo; Cappellini, Giancarlo; Satta, Guido; Porceddu, Ignazio; Benvenuti, Piero

    2004-05-01

    A theoretical study of rotational profiles of molecular absorption bands is essential for direct comparison with observations of diffuse interstellar bands. Applications using gaussian quantum-chemical approach within DFT are presented. Structural and vibrational properties of the polycyclic aromatic hydrocarbon ovalene cation (C32H14+) are obtained. We discuss the expected profile of the first electronic transition of such molecule, obtained with a Monte Carlo model of its rotation in the physical conditions of low temperatures and absence of collisions which are characteristic of the interstellar medium (ISM).

  9. Probing Warm Dense Matter electronic structure using X-ray absorption Near Edge Spectroscopy (XANES)

    NASA Astrophysics Data System (ADS)

    Benuzzi Mounaix, Alessandra

    2011-06-01

    The behavior and physical properties of warm dense matter, fundamental for various branches of physics including planetology and Inertial Confinement Fusion, are non trivial to simulate either theoretically, numerically or experimentally. Despite important progress obtained in the last decade on macroscopic characterization (e.g. equations of state), microscopic studies are today necessary to investigate finely the WDM structure changes, the phase transitions and to test physical hypothesis and approximations commonly used in calculations. In this work, highly compressed aluminum has been investigated with the aim of bringing information on the evolution of its electronic structure by using K-edge shift and XANES. The experiment was performed at LULI laboratory where we used one long pulse (500 ps, IL ~ 8 1013 W/cm2) to create a uniform shock and a second ps beam (IL ~ 1017 W/cm2) to generate an ultra-short broadband X-ray source near the Al K-edge. The spectra were registered by using two conical KAP Bragg crystals. The main target was designed to probe the Aluminum in reshocked conditions allowing us to probe and to test theories in an extreme regime up to now unexplored (ρ ~ 3 ρ0 and T ~ 8 eV). The hydrodynamical Al conditions were measured by using VISARs interferometers and self-emission diagnostics. By increasing the delay between the two beams, we have been able to observe the modification of absorption spectra for unloading Al conditions (ρ >= 0.5 g/cc), and to put in evidence the relocalization of the 3p valence electrons occurring in the metal-non metal transition. All data have been compared to ab initio and dense plasma calculations.

  10. Band edge engineering of oxide photoanodes for photoelectrochemical water splitting: Integration of subsurface dipoles with atomic-scale control

    DOE PAGESBeta

    Hikita, Yasuyuki; Nishio, Kazunori; Seitz, Linsey C.; Chakthranont, Pongkarn; Tachikawa, Takashi; Jaramillo, Thomas F.; Hwang, Harold Y.

    2016-01-22

    One of the crucial parameters dictating the efficiency of photoelectrochemical water-splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb-doped SrTiO3/aqueous electrolyte interface is reported. Lastly, the tunable range achieved farmore » exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.« less

  11. Intense laser field and conduction band-edge nonparabolicity effects on hydrogenic impurity states of InGaN QW

    NASA Astrophysics Data System (ADS)

    El Ghazi, Haddou

    2015-09-01

    In this paper, hydrogenic impurity ground-state binding energy in unstrained wurtzite (In, Ga)N symmetric quantum well is investigated. The heterostructure is considered under the action of an intense laser field (ILF) incorporating an additional internal probe as well as the conduction band-edge nonparabolicity effect (CBENP). The variational approach is used within the framework of single band effective-mass approximation with two-parametric 1S-hydrogenic trial wavefunction. The competition effect between internal and external perturbations is also shown. Our results reveal that the binding energy is the largest for the well width around the effective Bohr radius and is strongly influenced by both parameters. Moreover, the principle effect of ILF (CBENP) is to reduce (enhance) the binding energy. It is found that the lift of the conduction band-edge can be easily eliminated by adjusting the ILF-parameter.

  12. Nature and evolution of the band-edge states in MoS2: From monolayer to bulk

    NASA Astrophysics Data System (ADS)

    Padilha, J. E.; Peelaers, H.; Janotti, A.; Van de Walle, C. G.

    2014-11-01

    Exploring two-dimensional layered materials, such as molybdenum disulfide (MoS2), for (opto)electronic applications requires detailed knowledge of their electronic band structures. Using first-principles calculations we trace the evolution of the band structure as a function of the number of layers, starting from a monolayer, which has a direct gap, to the bulk material, which has an indirect gap. We find that, with respect to the vacuum level, the valence-band maximum (VBM) increases rapidly with the number of layers, while the conduction-band minimum (CBM) remains almost constant. For two or more layers the VBM always occurs at Γ and the CBM occurs at K. These findings are analyzed in terms of the orbital composition of the valence- and conduction-band edges at the various high-symmetry points in the Brillouin zone.

  13. 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.

  14. Quantitative analysis of deconvolved X-ray absorption near-edge structure spectra: a tool to push the limits of the X-ray absorption spectroscopy technique.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Persson, Ingmar; Mancini, Giordano; Della Longa, Stefano

    2014-09-15

    A deconvolution procedure has been applied to K-edge X-ray absorption near-edge structure (XANES) spectra of lanthanoid-containing solid systems, namely, hexakis(dmpu)praseodymium(III) and -gadolinium(III) iodide. The K-edges of lanthanoids cover the energy range 38 (La)-65 (Lu) keV, and the large widths of the core-hole states lead to broadening of spectral features, reducing the content of structural information that can be extracted from the raw X-ray absorption spectra. Here, we demonstrate that deconvolution procedures allow one to remove most of the instrumental and core-hole lifetime broadening in the K-edge XANES spectra of lanthanoid compounds, highlighting structural features that are lost in the raw data. We show that quantitative analysis of the deconvolved K-edge XANES spectra can be profitably used to gain a complete local structural characterization of lanthanoid-containing systems not only for the nearest neighbor atoms but also for higher-distance coordination shells. PMID:25171598

  15. Link between K absorption edges and thermodynamic properties of warm dense plasmas established by an improved first-principles method

    NASA Astrophysics Data System (ADS)

    Zhang, Shen; Zhao, Shijun; Kang, Wei; Zhang, Ping; He, Xian-Tu

    2016-03-01

    A precise calculation that translates shifts of x-ray K absorption edges to variations of thermodynamic properties allows quantitative characterization of interior thermodynamic properties of warm dense plasmas by x-ray absorption techniques, which provides essential information for inertial confinement fusion and other astrophysical applications. We show that this interpretation can be achieved through an improved first-principles method. Our calculation shows that the shift of K edges exhibits selective sensitivity to thermal parameters and thus would be a suitable temperature index to warm dense plasmas. We also show with a simple model that the shift of K edges can be used to detect inhomogeneity inside warm dense plasmas when combined with other experimental tools.

  16. An alternative model for photodynamic therapy of cancers: Hot-band absorption

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Chen, Jiyao

    2013-12-01

    The sulfonated aluminum phthalocyanine (AlPcS), a photosensitizer for photodynamic cancer therapy (PDT), has an absorption tail in the near-infrared region (700-900 nm) which is so-called hot band absorption (HBA). With the HBA of 800 nm, the up-conversion excitation of AlPcS was achieved followed by the anti-Stocks emission (688 nm band) and singlet oxygen production. The HBA PDT of AlPcS seriously damaged the KB and HeLa cancer cells, with a typical light dose dependent mode. Particularly, the in vitro experiments with the AlPcS shielding solutions further showed that the HBA PDT can overcome a self-shielding effect benefiting the PDT applications.

  17. Parallel LC circuit model for multi-band absorption and preliminary design of radiative cooling.

    PubMed

    Feng, Rui; Qiu, Jun; Liu, Linhua; Ding, Weiqiang; Chen, Lixue

    2014-12-15

    We perform a comprehensive analysis of multi-band absorption by exciting magnetic polaritons in the infrared region. According to the independent properties of the magnetic polaritons, we propose a parallel inductance and capacitance(PLC) circuit model to explain and predict the multi-band resonant absorption peaks, which is fully validated by using the multi-sized structure with identical dielectric spacing layer and the multilayer structure with the same strip width. More importantly, we present the application of the PLC circuit model to preliminarily design a radiative cooling structure realized by merging several close peaks together. This omnidirectional and polarization insensitive structure is a good candidate for radiative cooling application. PMID:25607485

  18. Collisional Induced Absorption (CIA) bands measured in the IR spectral range .

    NASA Astrophysics Data System (ADS)

    Stefani, S.; Piccioni, G.; Snels, M.; Adriani, A.; Grassi, D.

    In this work we present two experimental setup able to characterize the optical properties of gases, in particular CO_2 and H_2, at typically planetary conditions. The apparatus consists of a Fourier Transform InfraRed (FT-IT) interferometer able to work in a wide spectral range, from 350 to 25000 cm-1 (0.4 to 29 mu m ) with a relatively high spectral resolution, from 10 to 0.07 cm-1. Two dedicated gas cells have been integrated with the FT-IR. The first, called High Pressure High Temperature (HP-HT), can support pressures up to 300 bar, temperatures up to 300oC and is characterized by an optical path of 2 cm. The second one, a Multi Pass (MP) absorption gas cell, is designed to have a variable optical path, from 2.5 to 30 m, can be heated up to 200o and operate at pressures up to 10 bar. In this paper, measurements of Collision-Induced Absorption (CIA) bands in carbon dioxide and hydrogen recorded in the InfraRed spectral range will be presented. In principle, linear symmetric molecules such as CO_2 and H_2 possess no dipole moment, but, even when the pressure is only a few bar, we have observed the Collisional Induced Absorption (CIA) bands. This absorption results from a short-time collisional interaction between molecules. The band integrated intensity shows a quadratic dependence versus density opposed to the absorption by isolated molecules, which follows Beer's law \\citep{Beer's}. This behaviour suggests an absorption by pairs rather than by individual molecules. The bands integrated intensities show a linear dependence vs square density according to \\citep {CIA Shape} and \\citep{CIA posi}. For what concerns the H_2 CIA bands, a preliminary comparison between simulated data obtained with the model described in \\citep{CIA H2}and measured, shows a good agreement. These processes are very relevant in the dense atmospheres of planets, such as those of Venus and Jupiter and also in extrasolar planets. A detailed knowledge of these contributions is very

  19. Nitric oxide γ band fluorescent scattering and self-absorption in the mesosphere and lower thermosphere

    NASA Astrophysics Data System (ADS)

    Stevens, Michael H.

    1995-08-01

    The fluorescent scattering of UV sunlight and self-absorption by the nitric oxide (NO) γ bands between 2000-2500 Å are quantified for the purpose of inferring NO density profiles as a function of altitude in the mesosphere and above. Rotational line emission rate factors and cross sections are calculated at a variety of temperatures. The observed variation of the solar spectrum across the γ bands and its effect on emission rate factors are explored by using irradiance measurements that resolve features down to 0.1 Å. The model also includes quenching by O2 and N2, multiple scattering, temperature effects, attenuation of the solar irradiance by O2 and ozone, and self-absorption with the summation of adjacent rotational features. Results indicate that for resonant γ bands, the rotational structure in emission is not symmetric to that in absorption so that as self-absorption increases the shape of the observed emission envelope changes. For γ(1,0) this is largely characterized by an increase in the integrated emission observed longward of 2151 Å compared to shortward. It is found that solar irradiances measured at 0.1 Å resolution decrease the calculated γ(1,0) and γ(0,0) band emission rate factors by less than 3% compared to those measured at 2 Å resolution. However, more Fraunhofer structure included in the calculation is reflected in the relative intensities of the rotational features. It is also found that extinction of the solar irradiance by ozone and quenching by O2 rapidly reduce the γ(1,0) emission rate factor with decreasing altitude below 60 km.

  20. 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.

  1. Near-Edge X-Ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T.M.; Fabbri, J.D.; Lee, J.R.I.; Schreiner, P.R.; Fokin, A.A.; Tkachenko, B.A.; Fokina, N.A.; Dahl, J.E.P.; Carlson, R.M.K.; Vance, A.L.; Yang, W.; Terminello, L.J.; Buuren, T.van; Melosh, N.A.

    2009-05-26

    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 and 0.16 {+-} 0.04 eV, respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different degrees 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 nanoparticles.

  2. 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.

  3. Iron near absorption edge X-ray spectroscopy at aqueous-membrane interfaces

    SciTech Connect

    Wang, Wenjie; Kuzmenko, Ivan; Vaknin, David

    2014-01-01

    Employing synchrotron X-ray scattering, we systematically determine the absorption near-edge spectra (XANES) of iron in its ferrous (Fe2+) and ferric (Fe3+) states both as ions in aqueous solutions and as they bind to form a single layer to anionic templates that consist of carboxyl or phosphate groups at aqueous/vapor interfaces. While the XANES of bulk iron ions show that the electronic state and coordination of iron complexes in the bulk are isotropic, the interfacial bound ions show a signature of a broken inversion-symmetry environment. The XANES of Fe2+ and Fe3+ in the bulk possess distinct profiles however, upon binding they practically exhibit similar patterns. This indicates that both bound ions settle into a stable electronic and coordination configuration with an effective fractional valence (for example, Fe[2+nu]+, 0 < nu < 1) at charged organic templates. Such two dimensional properties may render interfacial iron, abundant in living organisms, a more efficient and versatile catalytic behavior.

  4. Analysis of the 4800-Å absorption band of Cs 2 by the classical method

    NASA Astrophysics Data System (ADS)

    Tellinghuisen, Joel; Moeller, Michael B.

    1980-09-01

    The broad absorption band in Cs 2 having peak intensity near 4800 Å is analyzed through computational simulation of the experimental spectrum using the classical method. The absorption, which terminates in a weak satellite at 5223 Å, can be interpreted in terms of a single transition from the ground state ( Re = 4.65 Å, ω e = 42 cm -1) to an upper state having Te = 20 470 cm -1, ω e = 33 cm -1 and Re = 5.28 Å. The absolute absorption strength is roughly consistent with published lifetime data, but its reliability is limited by thermodynamic uncertainties stemming from the remaining uncertainty in the Cs 2 ground state dissociation enegy. The paper includes a summary of diatomic radiation relations pertinent to the analysis of low-resolution spectra, and a brief discussion of the reduced potential method applied to the alkali dimer ground states.

  5. Decomposing the First Absorption Band of OCS Using Photofragment Excitation Spectroscopy.

    PubMed

    Toulson, Benjamin W; Murray, Craig

    2016-09-01

    Photofragment excitation spectra of carbonyl sulfide (OCS) have been recorded from 212-260 nm by state-selectively probing either electronically excited S((1)D) or ground state S((3)P) photolysis products via 2 + 1 resonance-enhanced multiphoton ionization. Probing the major S((1)D) product results in a broad, unstructured action spectrum that reproduces the overall shape of the first absorption band. In contrast, spectra obtained probing S((3)P) products display prominent resonances superimposed on a broad continuum; the resonances correspond to the diffuse vibrational structure observed in the conventional absorption spectrum. The vibrational structure is assigned to four progressions, each dominated by the C-S stretch, ν1, following direct excitation to quasi-bound singlet and triplet states. The S((3)PJ) products are formed with a near-statistical population distribution over the J = 2, 1, and 0 spin-orbit levels across the wavelength range investigated. Although a minor contributor to the S atom yield near the peak of the absorption cross section, the relative yield of S((3)P) increases significantly at longer wavelengths. The experimental measurements validate recent theoretical work characterizing the electronic states responsible for the first absorption band by Schmidt and co-workers. PMID:27552402

  6. Ultra-low-noise transition edge sensors for the SAFARI L-band on SPICA

    NASA Astrophysics Data System (ADS)

    Goldie, D. J.; Gao, J. R.; Glowacka, D. M.; Griffin, D. K.; Hijmering, R.; Khosropanah, P.; Jackson, B. D.; Mauskopf, P. D.; Morozov, D.; Murphy, J. A.; Ridder, M.; Trappe, N.; O'Sullivan, C.; Withington, S.

    2012-09-01

    The Far-Infrared Fourier transform spectrometer instrument SAFARI-SPICA which will operate with cooled optics in a low-background space environment requires ultra-sensitive detector arrays with high optical coupling efficiencies over extremely wide bandwidths. In earlier papers we described the design, fabrication and performance of ultra-low-noise Transition Edge Sensors (TESs) operated close to 100mk having dark Noise Equivalent Powers (NEPs) of order 4 × 10-19W/√Hz close to the phonon noise limit and an improvement of two orders of magnitude over TESs for ground-based applications. Here we describe the design, fabrication and testing of 388-element arrays of MoAu TESs integrated with far-infrared absorbers and optical coupling structures in a geometry appropriate for the SAFARI L-band (110 - 210 μm). The measured performance shows intrinsic response time τ ~ 11ms and saturation powers of order 10 fW, and a dark noise equivalent powers of order 7 × 10-19W/√Hz. The 100 × 100μm2 MoAu TESs have transition temperatures of order 110mK and are coupled to 320×320μm2 thin-film β-phase Ta absorbers to provide impedance matching to the incoming fields. We describe results of dark tests (i.e without optical power) to determine intrinsic pixel characteristics and their uniformity, and measurements of the optical performance of representative pixels operated with flat back-shorts coupled to pyramidal horn arrays. The measured and modeled optical efficiency is dominated by the 95Ω sheet resistance of the Ta absorbers, indicating a clear route to achieve the required performance in these ultra-sensitive detectors.

  7. Characterization of Oxygen Containing Functional Groups on Carbon Materials with Oxygen K-edge X-ray Absorption Near Edge Structure Spectroscopy

    SciTech Connect

    K Kim; P Zhu; L Na; X Ma; Y Chen

    2011-12-31

    Surface functional groups on carbon materials are critical to their surface properties and related applications. Many characterization techniques have been used to identify and quantify the surface functional groups, but none is completely satisfactory especially for quantification. In this work, we used oxygen K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify and quantify the oxygen containing surface functional groups on carbon materials. XANES spectra were collected in fluorescence yield mode to minimize charging effect due to poor sample conductivity which can potentially distort XANES spectra. The surface functional groups are grouped into three types, namely carboxyl-type, carbonyl-type, and hydroxyl-type. XANES spectra of the same type are very similar while spectra of different types are significantly different. Two activated carbon samples were analyzed by XANES. The total oxygen contents of the samples were estimated from the edge step of their XANES spectra, and the identity and abundance of different functional groups were determined by fitting of the sample XANES spectrum to a linear combination of spectra of the reference compounds. It is concluded that oxygen K-edge XANES spectroscopy is a reliable characterization technique for the identification and quantification of surface functional groups on carbon materials.

  8. Electronic structure and optical properties of CdS{sub x}Se{sub 1−x} solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

    SciTech Connect

    Murphy, M. W.; Yiu, Y. M. Sham, T. K.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai

    2014-11-21

    The electronic structure and optical properties of a series of iso-electronic and iso-structural CdS{sub x}Se{sub 1−x} solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

  9. Sensitivity analysis of oxygen absorption lines in the 1.26-1.27 micron spectral band

    NASA Astrophysics Data System (ADS)

    Edwards, W. C.; Prasad, N.; Browell, E. V.

    2009-12-01

    In the Decadal Survey prepared by the National Research Council (Reference: Earth Science and Applications from Space: National Imperatives for the Next Decade and Beyond), the ASCENDS mission (Active Sensing of CO2 Emissions over Nights, Days and Seasons), requires simultaneous laser remote sensing of CO2 and O2 in order to convert CO2 atmospheric concentrations to mixing ratios. As the mission is envisioned, the CO2 mixing ratio needs to be measured to a precision of 0.5 percent of background or better (slightly less than 2 ppm) at 100-km horizontal length scale overland and at 200-km scale over open oceans. While the O2 measurement could be made at 0.765 µm (the oxygen A band), the absorption cross section is substantially higher and the scattering is lower in the 1.26-1.27 µm wavelength band, and as such it is anticipated that better accuracies could be accomplished. Hence, NASA Langley Research Center is developing oxygen lidar technology in the 1.26-1.27 micron band for surface pressure measurements. One or more wavelengths for differential absorption lidar operation have to be carefully chosen to eliminate ambient influences on them. The model optical depth calculation is very sensitive to knowledge of the transmitted wavelengths and to the choice of Voigt input parameters. Uncertainties in atmospheric profiles of temperature, pressure and relative humidity can cause ~0.5 % errors in model optical depths. In order to select candidate wavelengths in the 1.26 micron spectral band, wavelength uncertainties due to temperature and pressure have to be determined. Uncertainties at line center and offset wavelengths have to be known precisely to reduce uncertainties in oxygen concentration measurements from airborne and space based platforms. In this paper, based on HITRAN database and absorption line measurements, we evaluate systematic relative errors and their sources of pressure shift and atmospheric temperature influences for selected O2 lines suitable for

  10. Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure.

    PubMed

    Yamaguchi, Noriko; Nakano, Masashi; Takamatsu, Rieko; Tanida, Hajime

    2010-06-01

    The transformation of inorganic iodine (I(-) and IO(3)(-)) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60d of reaction, both I(-) and IO(3)(-) were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO(3)(-) remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO(3)(-) into organoiodine was not retarded when the microbial activity in soil was reduced by gamma-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine. PMID:18640749

  11. Structural changes of nucleic acid base in aqueous solution as observed in X-ray absorption near edge structure (XANES)

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    X-ray absorption near edge structure (XANES) spectra for adenine-containing nucleotides, adenosine 5‧-monophosphate (AMP) and adenosine 5‧-triphosphate (ATP) in aqueous solutions at the nitrogen K-edge region were measured. The two intense peaks in XANES spectra are assigned to transitions of 1s electrons to the π∗ orbitals of different types of N atoms with particular bonding characteristics. The difference between their spectra is ascribed to protonation of a particular N atom. Similarity observed in XANES spectra of guanosine 5‧-monophosphate (GMP) and ATP is also interpreted as similar bonding characters of the N atoms in the nucleobase moiety.

  12. 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.

  13. Angle-resolved x-ray absorption near edge structure study of vertically aligned single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Li, Zhongrui; Zhang, Liang; Resasco, Daniel E.; Mun, Bongjin Simon; Requejo, Félix G.

    2007-03-01

    Vertically aligned single-walled carbon nanotube (SWNT) forest was studied by using angular-dependent C K-edge x-ray absorption near edge structure (XANES) with linearly polarized x-ray beam. The XANES analysis found a crust of entangled nanotubes on top of the forest formed at the first stage of the forest growth, which shapes the morphology of the entire forest and constricts the nanotubes to grow to the same length. It indicates that this type of SWNT forest has a different growth mechanism from the multiwalled carbon nanotube forest.

  14. Specular Andreev reflection at the edge of an InAs/GaSb double quantum well with band inversion

    NASA Astrophysics Data System (ADS)

    Kononov, A.; Egorov, S. V.; Kostarev, V. A.; Semyagin, B. R.; Preobrazhenskii, V. V.; Putyato, M. A.; Emelyanov, E. A.; Deviatov, E. V.

    2016-07-01

    We experimentally investigate transport through the side junction between a niobium superconductor and the mesa edge of a two-dimensional system, realized in an InAs/GaSb double quantum well with band inversion. We demonstrate, that different transport regimes can be achieved by variation of the mesa step. We observe anomalous behavior of Andreev reflection within a finite low-bias interval, which is invariant for both transport regimes. We connect this behavior with the transition from retro- (at low biases) to specular (at high ones) Andreev reflection channels in an InAs/GaSb double quantum well with band inversion.

  15. Electronic absorption band broadening and surface roughening of phthalocyanine double layers by saturated solvent vapor treatment

    SciTech Connect

    Kim, Jinhyun; Yim, Sanggyu

    2012-10-15

    Variations in the electronic absorption (EA) and surface morphology of three types of phthalocyanine (Pc) thin film systems, i.e. copper phthalocyanine (CuPc) single layer, zinc phthalocyanine (ZnPc) single layer, and ZnPc on CuPc (CuPc/ZnPc) double layer film, treated with saturated acetone vapor were investigated. For the treated CuPc single layer film, the surface roughness slightly increased and bundles of nanorods were formed, while the EA varied little. In contrast, for the ZnPc single layer film, the relatively high solubility of ZnPc led to a considerable shift in the absorption bands as well as a large increase in the surface roughness and formation of long and wide nano-beams, indicating a part of the ZnPc molecules dissolved in acetone, which altered their molecular stacking. For the CuPc/ZnPc film, the saturated acetone vapor treatment resulted in morphological changes in mainly the upper ZnPc layer due to the significantly low solubility of the underlying CuPc layer. The treatment also broadened the EA band, which involved a combination of unchanged CuPc and changed ZnPc absorption.

  16. Regional estimation of savanna grass nitrogen using the red-edge band of the spaceborne RapidEye sensor

    NASA Astrophysics Data System (ADS)

    Ramoelo, A.; Skidmore, A. K.; Cho, M. A.; Schlerf, M.; Mathieu, R.; Heitkönig, I. M. A.

    2012-10-01

    The regional mapping of grass nutrients is of interest in the sustainable planning and management of livestock and wildlife grazing. The objective of this study was to estimate and map foliar and canopy nitrogen (N) at a regional scale using a recent high resolution spaceborne multispectral sensor (i.e. RapidEye) in the Kruger National Park (KNP) and its surrounding areas, South Africa. The RapidEye sensor contains five spectral bands in the visible-to-near infrared (VNIR), including a red-edge band centered at 710 nm. The importance of the red-edge band for estimating foliar chlorophyll and N concentrations has been demonstrated in many previous studies, mostly using field spectroscopy. The utility of the red-edge band of the RapidEye sensor for estimating grass N was investigated in this study. A two-step approach was adopted involving (i) vegetation indices and (ii) the integration of vegetation indices with environmental or ancillary variables using a stepwise multiple linear regression (SMLR) and a non-linear spatial least squares regression (PLSR). The model involving the simple ratio (SR) index (R805/R710) defined as SR54, altitude and the interaction between SR54 and altitude (SR54 * altitude) yielded the highest accuracy for canopy N estimation, while the non-linear PLSR yielded the highest accuracy for foliar N estimation through the integration of remote sensing (SR54) and environmental variables. The study demonstrated the possibility to map grass nutrients at a regional scale provided there is a spaceborne sensor encompassing the red edge waveband with a high spatial resolution.

  17. Enhanced band-edge photoluminescence from ZnO-passivated ZnO nanoflowers by atomic layer deposition

    PubMed Central

    2013-01-01

    The ZnO nanoflowers were synthesized by reactive vapor deposition. A secondary nucleation in the stalk/leaves interface was suggested. The photoluminescence revealed that there were many oxygen vacancies in the nanoflowers. To tune the optical properties of ZnO nanoflowers, ZnO thin films with varying thicknesses were coated on the nanoflowers by atomic layer deposition, which can distinctly improve the band-edge photoluminescence properties. PMID:23442577

  18. Imaging Breathing Rate in the CO2Absorption Band.

    PubMed

    Fei, Jin; Zhu, Zhen; Pavlidis, Ioannis

    2005-01-01

    Following up on our previous work, we have developed one more non-contact method to measure human breathing rate. We have retrofitted our Mid-Wave Infra-Red (MWIR) imaging system with a narrow band-pass filter in the CO2absorption band (4.3 µm). This improves the contrast between the foreground (i.e., expired air) and background (e.g., wall). Based on the radiation information within the breath flow region, we get the mean dynamic thermal signal. This signal is quasi-periodic due to the interleaving of high and low intensities corresponding to expirations and inspirations respectively. We sample the signal at a constant rate and then determine the breathing frequency through Fourier analysis. We have performed experiments on 9 subjects at distances ranging from 6-8 ft. We compared the breathing rate computed by our novel method with ground-truth measurements obtained via a traditional contact device (PowerLab/4SP from ADInstruments with an abdominal transducer). The results show high correlation between the two modalities. For the first time, we report a Fourier based breathing rate computation method on a MWIR signal in the CO2absorption band. The method opens the way for desktop, unobtrusive monitoring of an important vital sign, that is, breathing rate. It may find widespread applications in preventive medicine as well as sustained physiological monitoring of subjects suffering from chronic ailments. PMID:17282279

  19. Infrared absorption band in deformed qtz crystals analyzed by combining different microstructural methods

    NASA Astrophysics Data System (ADS)

    Stunitz, Holger; Thust, Anja; Behrens, Harald; Heilbronner, Renee; Kilian, Ruediger

    2016-04-01

    Natural single crystals of quartz have been experimentally deformed in two orientations: (1) normal to one prism-plane, (2) In O+ orientation at temperatures of 900 and 1000°C, pressures of 1.0 and 1.5 GPa, and strain rates of ~1 x 10-6s-1. The starting material is milky quartz, consisting of dry quartz (H2O contents of <150 H/106Si) with fluid inclusions (FI). During pressurization many FÍs decrepitate. Cracks heal and small neonate FÍs form, increasing the number of FÍs drastically. During subsequent deformation, the size of FÍs is further reduced (down to ~10 nm). Sample deformation occurs by dominant dislocation glide on selected slip systems, accompanied by some dynamic recovery. Strongly deformed regions show FTIR spectra with a pointed broad absorption band in the ~3400 cm-1 region as a superposition of molecular H2O bands and three discrete absorption bands (at 3367, 3400, and 3434 cm-1). In addition, there is a discrete absorption band at 3585 cm-1, which only occurs in deformed regions. The 3585 cm-1 band is reduced or even disappears after annealing. This band is polarized and represents structurally bound H, its H-content is estimated to be 1-3% of the total H2O-content and appears to be associated with dislocations. The H2O weakening effect in our FI-bearing natural quartz crystals is assigned to the processes of dislocation generation and multiplication at small FÍs. The deformation processes in these crystals represent a recycling of H2O between FÍs, dislocation generation at very small fluid inclusions, incorporation of structurally bound H into dislocation cores, and release of H2O from dislocations back into FÍs during recovery. Cracking and crack healing play an important role in the recycling process and imply a close interrelationship between brittle and crystal plastic deformation. The H2O weakening by this process is of a disequilibrium nature and thus depends on the amount of H2O available.

  20. Atomic form factors and photoelectric absorption cross-sections near absorption edges in the soft X-ray region

    NASA Astrophysics Data System (ADS)

    Chantler, C. T.

    2003-01-01

    Reliable knowledge of the complex X-ray form factor [Re(f) and Im(f)] and the photoelectric attenuation coefficient (σPE) 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].

  1. THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. II. X-RAY ABSORPTION EDGE STUDIES ON MANGANESE IN PHOTOSYNTHETIC MEMBRANES

    SciTech Connect

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

    1980-11-01

    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. 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.

  2. Concentration measurement of NO using self-absorption spectroscopy of the γ band system in a pulsed corona discharge.

    PubMed

    Zhai, Xiaodong; Ding, Yanjun; Peng, Zhimin; Luo, Rui

    2012-07-10

    Nitric oxide (NO) concentrations were measured using the γ band system spectrum based on the strong self-absorption effect of NO in pulsed corona discharges. The radiative transitional intensities of the NO γ band were simulated based on the theory of molecular spectroscopy. The intensities of some bands, especially γ(0,0) and γ(1,0), are weakened by the self-absorption. The correlations between the spectral self-absorption intensities and NO concentration were validated using a modified Beer-Lambert law with a combined factor K relating the branching ratio and the NO concentration, and a nonlinear index α that is applicable to the broadband system. Optical emissive spectra in pulsed corona discharges in NO and N2/He mixtures were used to evaluate the two parameters for various conditions. Good agreement between the experimental and theoretical results verifies the self-absorption behavior seen in the UV spectra of the NO γ bands. PMID:22781235

  3. Ab initio x-ray absorption study of copper K-edge XANES spectra in Cu(II) compounds

    SciTech Connect

    Chaboy, Jesus; Munoz-Paez, Adela; Carrera, Flora; Merkling, Patrick; Marcos, Enrique Sanchez

    2005-04-01

    This work reports a theoretical study of the x-ray absorption near-edge structure spectra at the Cu K edge in several Cu(II) complexes with N-coordinating ligands showing a square-planar arrangement around metal cation. It is shown that single-channel multiple-scattering calculations are not able to reproduce the experimental spectra. The comparison between experimental data and ab initio computations indicates the need of including the contribution of two electronic configurations (3d{sup 9} and 3d{sup 10}L) to account for a proper description of the final state during the photoabsorption process. The best agreement between theory and experiment is obtained by considering a relative weight of 68% and 32% for the two absorption channels 3d{sup 10}L and 3d{sup 9}, respectively.

  4. Sulfur 1s near-edge x-ray absorption fine structure (NEXAFS) of thiol and thioether compounds

    SciTech Connect

    Beyhan, Shirin; Urquhart, Stephen G.; Hu Yongfeng

    2011-06-28

    The speciation and quantification of sulfur species based on sulfur K-edge x-ray absorption spectroscopy is of wide interest, particularly for biological and petroleum science. These tasks require a firm understanding of the sulfur 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of relevant species. To this end, we have examined the gas phase sulfur 1s NEXAFS spectra of a group of simple thiol and thioether compounds. These high-resolution gas phase spectra are free of solid-state broadening, charging, and saturation effects common in the NEXAFS spectra of solids. These experimental data have been further analyzed with the aid of improved virtual orbital Hartree-Fock ab initio calculations. The experimental sulfur 1s NEXAFS spectra show fine features predicted by calculation, and the combination of experiment and calculation has been used to improve assignment of spectroscopic features relevant for the speciation and quantification of the sulfur compounds.

  5. Optical absorption and band gap reduction in (Fe1-xCrx)2O3 solid solutions: A first-principles study

    SciTech Connect

    Wang, Yong; Lopata, Kenneth A.; Chambers, Scott A.; Govind, Niranjan; Sushko, Petr V.

    2013-12-02

    We provide a detailed theoretical analysis of the character of optical transitions and band gap reduction in (Fe1-xCrx)2O3 solid solutions using extensive periodic model and embedded cluster calculations. Optical absorption bands for x = 0.0, 0.5, and 1.0 are assigned on the basis of timedependent density functional theory (TDDFT) calculations. A band-gap reduction of as much as 0.7 eV with respect to that of pure α-Fe2O3 is found. This result can be attributed to predominantly two effects: (i) the higher valence band edge for x ≈ 0.5, as compared to those in pure α-Fe2O3 and α-Cr2O3, and, (ii) the appearance of Cr  Fe d–d transitions in the solid solutions. Broadening of the valence band due to hybridization of the O 2p states with Fe and Cr 3d states also contributes to band gap reduction.

  6. Origin of the red shifts in the optical absorption bands of nonplanar tetraalkylporphyrins.

    PubMed

    Haddad, Raid E; Gazeau, Stéphanie; Pécaut, Jacques; Marchon, Jean-Claude; Medforth, Craig J; Shelnutt, John A

    2003-02-01

    The view that the large red shifts seen in the UV-visible absorption bands of peripherally crowded nonplanar porphyrins are the result of nonplanar deformations of the macrocycle has recently been challenged by the suggestion that the red shifts arise from substituent-induced changes in the macrocycle bond lengths and bond angles, termed in-plane nuclear reorganization (IPNR). We have analyzed the contributions to the UV-visible band shifts in a series of nickel or zinc meso-tetraalkylporphyrins to establish the origins of the red shifts in these ruffled porphyrins. Structures were obtained using a molecular mechanics force field optimized for porphyrins, and the nonplanar deformations were quantified by using normal-coordinate structural decomposition (NSD). Transition energies were calculated by the INDO/S semiempirical method. These computational studies demonstrate conclusively that the large Soret band red shifts ( approximately 40 nm) seen for very nonplanar meso-tetra(tert-butyl)porphyrin compared to meso-tetra(methyl)porphyrin are primarily the result of nonplanar deformations and not IPNR. Strikingly, nonplanar deformations along the high-frequency 2B(1u) and 3B(1u) normal coordinates of the macrocycle are shown to contribute significantly to the observed red shifts, even though these deformations are an order of magnitude smaller than the observed ruffling (1B(1u)) deformation. Other structural and electronic influences on the UV-visible band shifts are discussed and problems with the recent studies are examined (e.g., the systematic underestimation of the 2B(1u) and 3B(1u) modes in artificially constrained porphyrin structures that leads to a mistaken attribution of the red shift to IPNR). The effect of nonplanar deformations on the UV-visible absorption bands is then probed experimentally with a series of novel bridled nickel chiroporphyrins. In these compounds, the substituent effect is essentially invariant and the amount of nonplanar deformation

  7. Ultra-narrow band perfect absorbers based on plasmonic analog of electromagnetically induced absorption.

    PubMed

    He, Jinna; Ding, Pei; Wang, Junqiao; Fan, Chunzhen; Liang, Erjun

    2015-03-01

    A novel plasmonic metamaterial consisting of the solid (bar) and the inverse (slot) compound metallic nanostructure for electromagnetically induced absorption (EIA) is proposed in this paper, which is demonstrated to achieve an ultra-narrow absorption peak with the linewidth less than 8 nm and the absorptivity exceeding 97% at optical frequencies. This is attributed to the plasmonic EIA resonance arising from the efficient coupling between the magnetic response of the slot (dark mode) and the electric resonance of the bar (bright mode). To the best of our knowledge, this is the first time that the plasmonic EIA is used to realize the narrow-band perfect absorbers. The underlying physics are revealed by applying the two-coupled-oscillator model. The near-perfect-absorption resonance also causes an enhancement of about 50 times in H-field and about 130 times in E-field within the slots. Such absorber possesses potential for applications in filter, thermal emitter, surface enhanced Raman scattering, sensing and nonlinear optics. PMID:25836832

  8. Theory of x-ray absorption and linear dichroism at the Ca L23-edge of CaCO3

    NASA Astrophysics Data System (ADS)

    Krüger, Peter; Natoli, Calogero R.

    2016-05-01

    X-ray absorption calculations of Ca L23-edge spectra of calcium carbonate in its two main crystal phases, calcite and aragonite, are reported. The multichannel multiple scattering theory with a correlated particle-hole wave function and a partially screened core-hole potential is used. Very good agreement with experiment for both CaCO3 phases is obtained, while the independent particle approximation completely fails. For aragonite, appreciable linear dichroism is predicted in agreement with recent observations.

  9. Collisional Induced Absorption (CIA) bands of CO2 and H2 measured in the IR spectral range

    NASA Astrophysics Data System (ADS)

    Stefani, S.; Piccioni, G.; Snels, M.; Adriani, A.; Grassi, D.

    2015-10-01

    In this paper we present the results on the Collisional Induced Absorption (CIA) bands of CO2 and H2 measured employing two different experimental setup. Each of them allows us to reproduce typical planetary conditions, at a pressure and temperature from 1 up to 50 bar and from 298 up to 500 K respectively. A detailed study on the temperature dependence of the CO2 CIA absorption bands will be presented.

  10. Theoretical reproduction of the Q-band absorption spectrum of free-base chlorin

    NASA Astrophysics Data System (ADS)

    Wójcik, Justyna; Ratuszna, Alicja; Peszke, Jerzy; Wrzalik, Roman

    2015-01-01

    The computational results of the features observed in the room-temperature Q-band absorption spectrum of free-base chlorin (H2Ch) are presented. The vibrational structures of the first and second excited singlet states were calculated based on a harmonic approximation using density functional theory and its time dependent extension within the Franck-Condon and Herzberg-Teller approaches. The outcome allowed to identify the experimental bands and to assign them to the specific vibrational transitions. A very good agreement between the simulated and measured wavelengths and their relative intensities provided the opportunity to predict the origin of the S0 → S2 transition which could not be determined experimentally.

  11. Theoretical reproduction of the Q-band absorption spectrum of free-base chlorin.

    PubMed

    Wójcik, Justyna; Ratuszna, Alicja; Peszke, Jerzy; Wrzalik, Roman

    2015-01-21

    The computational results of the features observed in the room-temperature Q-band absorption spectrum of free-base chlorin (H2Ch) are presented. The vibrational structures of the first and second excited singlet states were calculated based on a harmonic approximation using density functional theory and its time dependent extension within the Franck-Condon and Herzberg-Teller approaches. The outcome allowed to identify the experimental bands and to assign them to the specific vibrational transitions. A very good agreement between the simulated and measured wavelengths and their relative intensities provided the opportunity to predict the origin of the S0 → S2 transition which could not be determined experimentally. PMID:25612704

  12. Study of sub band gap absorption of Sn doped CdSe thin films

    NASA Astrophysics Data System (ADS)

    Kaur, Jagdish; Rani, Mamta; Tripathi, S. K.

    2014-04-01

    The nanocrystalline thin films of Sn doped CdSe at different dopants concentration are prepared by thermal evaporation technique on glass substrate at room temperature. The effect of Sn doping on the optical properties of CdSe has been studied. A decrease in band gap value is observed with increase in Sn concentration. Constant photocurrent method (CPM) is used to study the absorption coefficient in the sub band gap region. Urbach energy has been obtained from CPM spectra which are found to increase with amount of Sn dopants. The refractive index data calculated from transmittance is used for the identification of oscillator strength and oscillator energy using single oscillator model which is found to be 7.7 and 2.12 eV, 6.7 and 2.5 eV for CdSe:Sn 1% and CdSe:Sn 5% respectively.

  13. Study of sub band gap absorption of Sn doped CdSe thin films

    SciTech Connect

    Kaur, Jagdish; Rani, Mamta; Tripathi, S. K.

    2014-04-24

    The nanocrystalline thin films of Sn doped CdSe at different dopants concentration are prepared by thermal evaporation technique on glass substrate at room temperature. The effect of Sn doping on the optical properties of CdSe has been studied. A decrease in band gap value is observed with increase in Sn concentration. Constant photocurrent method (CPM) is used to study the absorption coefficient in the sub band gap region. Urbach energy has been obtained from CPM spectra which are found to increase with amount of Sn dopants. The refractive index data calculated from transmittance is used for the identification of oscillator strength and oscillator energy using single oscillator model which is found to be 7.7 and 2.12 eV, 6.7 and 2.5 eV for CdSe:Sn 1% and CdSe:Sn 5% respectively.

  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. 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.

  16. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

    DOE PAGESBeta

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2014-08-11

    Here, we report that the reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.

  17. Thermochromic Absorption, Fluorescence Band Shifts and Dipole Moments of BADAN and ACRYLODAN

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2002-08-01

    Using the thermochromic shift method of absorption and fluorescence bands, the electric dipole moments in the ground (μg) and excited (μe) state are simultaneously determined for BADAN (6-bromoacetyl-2-dimethylamino-naphtalene) and ACRYLODAN (6-acrylolyl-2-dimethylamino-naphtalene) in ethyl acetate. For these compounds the same ratio μe/μg = 2.9 was found, which is similar to that of PRODAN (6-propionyl-2-dimethylamino-naphtalene). The estimated empirical Onsager radii afor BADAN and ACRYLODAN are the same, and they are somewhat smaller than the calculated geometrical values.

  18. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

    SciTech Connect

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2014-08-11

    Here, we report that the reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.

  19. Theoretical Modeling of Low Energy Electronic Absorption Bands in Reduced Cobaloximes

    PubMed Central

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2015-01-01

    The reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task. PMID:25113847

  20. Femtosecond supercontinuum generation in water in the vicinity of absorption bands.

    PubMed

    Dharmadhikari, J A; Steinmeyer, G; Gopakumar, G; Mathur, D; Dharmadhikari, A K

    2016-08-01

    We show that it is possible to overcome the perceived limitations caused by absorption bands in water so as to generate supercontinuum (SC) spectra in the anomalous dispersion regime that extend well beyond 2000 nm wavelength. By choosing a pump wavelength within a few hundred nanometers above the zero-dispersion wavelength of 1048 nm, initial spectral broadening extends into the normal dispersion regime and, in turn, the SC process in the visible strongly benefits from phase-matching and matching group velocities between dispersive radiation and light in the anomalous dispersion regime. Some of the SC spectra are shown to encompass two and a half octaves. PMID:27472597

  1. Temperature-dependent dielectric function of bulk SrTiO3: Urbach tail, band edges, and excitonic effects

    NASA Astrophysics Data System (ADS)

    Gogoi, Pranjal Kumar; Schmidt, Daniel

    2016-02-01

    We report the temperature-dependent complex dielectric function of pristine bulk SrTiO3 between 4.2 and 300 K within the energy range of 0.6-6.5 eV determined by spectroscopic ellipsometry. Fundamental indirect and direct band-gap energies have been extracted and are discussed with regard to existing state-of-the-art theoretical calculations. Furthermore, the dielectric function around the fundamental direct gap is analyzed by considering excitonic states. The excitonic effects, including the Coulomb enhancement of the continuum, are characterized using an extension of the Elliott's formula considering both the real and imaginary parts of the dielectric function. The Urbach tail below the indirect edge shows an unconventional temperature-dependent behavior correlated to the microstructural changes near the structural phase transition around 105 K from the low-temperature tetragonal phase to the cubic phase. The temperature-dependent characterization reveals that the fundamental indirect edge as well as the Urbach tail are affected conspicuously by the structural phase transition while the fundamental direct edge is not. Moreover, the indirect edge follows Varshni's rule only in the cubic phase and the direct edge exhibits an anomalous linear increase with increasing temperature.

  2. 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.

  3. Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

    NASA Astrophysics Data System (ADS)

    Bhattacherjee, Aditi; Attar, Andrew R.; Leone, Stephen R.

    2016-03-01

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH2 =CHCH2I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground (2P3/2, I) and spin-orbit excited (2P1/2, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N4/5 edge (45-60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive nIσ∗C—I excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ∗ states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ∗(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs-65 fs and decay completely by 145 fs-185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic structure in the transition state region. The results provide a benchmark for

  4. Mechanism of Pressure-Induced Phase Transitions, Amorphization, and Absorption-Edge Shift in Photovoltaic Methylammonium Lead Iodide.

    PubMed

    Szafrański, Marek; Katrusiak, Andrzej

    2016-09-01

    Our single-crystal X-ray diffraction study of methylammonium lead triiodide, MAPbI3, provides the first comprehensive structural information on the tetragonal phase II in the pressure range to 0.35 GPa, on the cubic phase IV stable between 0.35 and 2.5 GPa, and on the isostructural cubic phase V observed above 2.5 GPa, which undergoes a gradual amorphization. The optical absorption study confirms that up to 0.35 GPa, the absorption edge of MAPbI3 is red-shifted, allowing an extension of spectral absorption. The transitions to phases IV and V are associated with the abrupt blue shifts of the absorption edge. The strong increase of the energy gap in phase V result in a spectacular color change of the crystal from black to red around 3.5 GPa. The optical changes have been correlated with the pressure-induced strain of the MAPbI3 inorganic framework and its frustration, triggered by methylammonium cations trapped at random orientations in the squeezed voids. PMID:27538989

  5. Linear-Circular Dichroism of Four-Photon Absorption of Light in Semiconductors with a Complex Valence Band

    NASA Astrophysics Data System (ADS)

    Rasulov, R. Ya.; Rasulov, V. R.; Eshboltaev, I.

    2016-04-01

    Matrix elements of optical transitions occuring between the subbands of the valence band of a p-GaAs type semiconductor are calculated. Transitions associated with the non-simultaneous absorption of single photons and simultaneous absorption of two photons are taken into account. The expressions are obtained for the average values of the square modulus of matrix elements calculated with respect to the solid angle of the wave vector of holes. Linear-circular dichroism of four-photon absorption of light in semiconductors with a complex valence band is theoretically studied.

  6. Absorption coefficients for the 6190-A CH4 band between 290 and 100 K with application to Uranus' atmosphere

    NASA Technical Reports Server (NTRS)

    Smith, Wm. Hayden; Conner, Charles P.; Baines, Kevin H.

    1990-01-01

    A novel laser intracavity photoacoustic spectroscopy method allowing high sample control accuracy due to the small sample volume required has been used to obtain absorption coefficients for the CH4 6190 A band as a function of temperature, from 290 to 100 K. The peak absorption coefficient is found to increase from 0.6 to 1.0/cm, and to be accompanied by significant band shape changes. When used to further constrain the Baines and Bergstrahl (1986) standard model of the Uranus atmosphere, the low-temperature data yield an excellent fit to the bandshape near the 6190 A band's minimum.

  7. Nanosecond light induced, thermally tunable transient dual absorption bands in a-Ge₅As₃₀Se₆₅ thin film.

    PubMed

    Khan, Pritam; Saxena, Tarun; Jain, H; Adarsh, K V

    2014-01-01

    In this article, we report the first observation of nanosecond laser induced transient dual absorption bands, one in the bandgap (TA₁) and another in the sub-bandgap (TA₂) regions of a-Ge₅As₃₀Se₆₅ thin films. Strikingly, these bands are thermally tunable and exhibit a unique contrasting characteristic: the magnitude of TA₁ decreases while that of TA₂ increases with increasing temperature. Further, the decay kinetics of these bands is strongly influenced by the temperature, which signifies a strong temperature dependent exciton recombination mechanism. The induced absorption shows quadratic and the decay time constant shows linear dependence on the laser beam fluence. PMID:25300520

  8. Absorption coefficients for the 6190-A CH sub 4 band between 290 and 100 K with application to Uranus' atmosphere

    SciTech Connect

    Smith, WM.H.; Conner, C.P.; Baines, K.H. JPL, Pasadena, CA )

    1990-05-01

    A novel laser intracavity photoacoustic spectroscopy method allowing high sample control accuracy due to the small sample volume required has been used to obtain absorption coefficients for the CH{sub 4} 6190 A band as a function of temperature, from 290 to 100 K. The peak absorption coefficient is found to increase from 0.6 to 1.0/cm, and to be accompanied by significant band shape changes. When used to further constrain the Baines and Bergstrahl (1986) standard model of the Uranus atmosphere, the low-temperature data yield an excellent fit to the bandshape near the 6190 A band's minimum. 18 refs.

  9. Ultra-wideband microwave absorber by connecting multiple absorption bands of two different-sized hyperbolic metamaterial waveguide arrays

    PubMed Central

    Yin, Xiang; Long, Chang; Li, Junhao; Zhu, Hua; Chen, Lin; Guan, Jianguo; Li, Xun

    2015-01-01

    Microwave absorbers have important applications in various areas including stealth, camouflage, and antenna. Here, we have designed an ultra-broadband light absorber by integrating two different-sized tapered hyperbolic metamaterial (HMM) waveguides, each of which has wide but different absorption bands due to broadband slow-light response, into a unit cell. Both the numerical and experimental results demonstrate that in such a design strategy, the low absorption bands between high absorption bands with a single-sized tapered HMM waveguide array can be effectively eliminated, resulting in a largely expanded absorption bandwidth ranging from 2.3 to 40 GHz. The presented ultra-broadband light absorber is also insensitive to polarization and robust against incident angle. Our results offer a further step in developing practical artificial electromagnetic absorbers, which will impact a broad range of applications at microwave frequencies. PMID:26477740

  10. Ultra-wideband microwave absorber by connecting multiple absorption bands of two different-sized hyperbolic metamaterial waveguide arrays

    NASA Astrophysics Data System (ADS)

    Yin, Xiang; Long, Chang; Li, Junhao; Zhu, Hua; Chen, Lin; Guan, Jianguo; Li, Xun

    2015-10-01

    Microwave absorbers have important applications in various areas including stealth, camouflage, and antenna. Here, we have designed an ultra-broadband light absorber by integrating two different-sized tapered hyperbolic metamaterial (HMM) waveguides, each of which has wide but different absorption bands due to broadband slow-light response, into a unit cell. Both the numerical and experimental results demonstrate that in such a design strategy, the low absorption bands between high absorption bands with a single-sized tapered HMM waveguide array can be effectively eliminated, resulting in a largely expanded absorption bandwidth ranging from 2.3 to 40 GHz. The presented ultra-broadband light absorber is also insensitive to polarization and robust against incident angle. Our results offer a further step in developing practical artificial electromagnetic absorbers, which will impact a broad range of applications at microwave frequencies.

  11. Ultra-wideband microwave absorber by connecting multiple absorption bands of two different-sized hyperbolic metamaterial waveguide arrays.

    PubMed

    Yin, Xiang; Long, Chang; Li, Junhao; Zhu, Hua; Chen, Lin; Guan, Jianguo; Li, Xun

    2015-01-01

    Microwave absorbers have important applications in various areas including stealth, camouflage, and antenna. Here, we have designed an ultra-broadband light absorber by integrating two different-sized tapered hyperbolic metamaterial (HMM) waveguides, each of which has wide but different absorption bands due to broadband slow-light response, into a unit cell. Both the numerical and experimental results demonstrate that in such a design strategy, the low absorption bands between high absorption bands with a single-sized tapered HMM waveguide array can be effectively eliminated, resulting in a largely expanded absorption bandwidth ranging from 2.3 to 40 GHz. The presented ultra-broadband light absorber is also insensitive to polarization and robust against incident angle. Our results offer a further step in developing practical artificial electromagnetic absorbers, which will impact a broad range of applications at microwave frequencies. PMID:26477740

  12. Thermally induced effect on sub-band gap absorption in Ag doped CdSe thin films

    NASA Astrophysics Data System (ADS)

    Kaur, Jagdish; Sharma, Kriti; Bharti, Shivani; Tripathi, S. K.

    2015-05-01

    Thin films of Ag doped CdSe have been prepared by thermal evaporation using inert gas condensation (IGC) method taking Argon as inert gas. The prepared thin films are annealed at 363 K for one hour. The sub-band gap absorption spectra in the as deposited and annealed thin films have been studied using constant photocurrent method (CPM). The absorption coefficient in the sub-band gap region is described by an Urbach tail in both as deposited and annealed thin films. The value of Urbach energy and number density of trap states have been calculated from the absorption coefficient in the sub-band gap region which have been found to increase after annealing treatment indicating increase in disorderness in the lattice. The energy distribution of the occupied density of states below Fermi level has also been studied using derivative procedure of absorption coefficient.

  13. 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. PMID:26651800

  14. Radiative ablation with two ionizing fronts when opacity displays a sharp absorption edge

    NASA Astrophysics Data System (ADS)

    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.

  15. Total ozone and aerosol optical depths inferred from radiometric measurements in the Chappuis absorption band

    SciTech Connect

    Flittner, D.E.; Herman, B.M.; Thome, K.J.; Simpson, J.M.; Reagan, J.A. )

    1993-04-15

    A second-derivative smoothing technique, commonly used in inversion work, is applied to the problem of inferring total columnar ozone amounts and aerosol optical depths. The application is unique in that the unknowns (i.e., total columnar ozone and aerosol optical depth) may be solved for directly without employing standard inversion methods. It is shown, however, that by employing inversion constraints, better solutions are normally obtained. The current method requires radiometric measurements of total optical depth through the Chappuis ozone band. It assumes no a priori shape for the aerosol optical depth versus wavelength profile and makes no assumptions about the ozone amount. Thus, the method is quite versatile and able to deal with varying total ozone and various aerosol size distributions. The technique is applied first in simulation, then to 119 days of measurements taken in Tucson, Arizona, that are compared to TOMS values for the same dates. The technique is also applied to two measurements taken at Mauna Loa, Hawaii, for which Dobson ozone values are available in addition to the TOMS values, and the results agree to within 15%. It is also shown through simulations that additional information can be obtained from measurements outside the Chappuis band. This approach reduces the bias and spread of the estimates total ozone and is unique in that it uses measurements from both the Chappuis and Huggins absorption bands. 12 refs., 6 figs., 2 tabs.

  16. Polarization-adjustable dual-band absorption in GHz-band metamaterial, based-on no-smoking symbol

    NASA Astrophysics Data System (ADS)

    Yoo, Young Joon; Kim, Young Ju; Lee, YoungPak; Lee, Myung Whan; Lee, Tae Gyun; Kim, Min Woo; Park, Jae Hyun

    2015-11-01

    We propose three kinds of the perfect metamaterial absorbers based on the well-known no-smoking symbol, which can adjust the absorption according to the polarization of incident electromagnetic wave. By modifying no-smoking symbol, a resonance absorption peak at 6.75 GHz can be controlled. In addition, a split-ring structure and the no-smoking symbol also adjust the absorption. We also demonstrate the absorption mechanism for all the structures. These results can be used in controlling absorption by the electromagnetic-wave detector.

  17. 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.

  18. Effect of N2 and H2 plasma treatments on band edge emission of ZnO microrods

    PubMed Central

    Rodrigues, Joana; Holz, Tiago; Fath Allah, Rabie; Gonzalez, David; Ben, Teresa; Correia, Maria R.; Monteiro, Teresa; Costa, Florinda M.

    2015-01-01

    ZnO microrods were grown by laser assisted flow deposition technique in order to study their luminescence behaviour in the near band edge spectral region. Transmission electron microscopy analysis put in evidence the high crystallinity degree and microrod’s compositional homogeneity. Photoluminescence revealed a dominant 3.31 eV emission. The correlation between this emission and the presence of surface states was investigated by performing plasma treatments with hydrogen and nitrogen. The significant modifications in photoluminescence spectra after the plasma treatments suggest a connexion between the 3.31 eV luminescence and the surface related electronic levels. PMID:26027718

  19. Tunability of the optical band edge in thin PbS films chemically deposited on GaAs(100).

    PubMed

    Osherov, Anna; Makai, Janos P; Balazs, Janos; Horvath, Zsolt J; Gutman, Nadav; Sa'ar, Amir; Golan, Yuval

    2010-07-01

    The optical properties of chemical-solution-deposited thin films of lead sulfide (PbS) were investigated using infrared transmission and photoluminescence spectroscopies. The synthesized films are characterized by a wide range of microstructures, from 15 nm nanocrystals up to monocrystals. Energy bandgap values for bulk and nanostructured layers varied from 0.41 eV up to 0.48 eV, respectively. Blueshifts in both absorbance and emission peaks of the nanostructured layers were obtained due to quantum size effects. The optical properties of the films are shown to be size-dependent, with the band edge increasing with temperature. PMID:21386454

  20. Electronic defect states at the LaAlO3/SrTiO3 heterointerface revealed by O K-edge X-ray absorption spectroscopy.

    PubMed

    Palina, Natalia; Annadi, Anil; Asmara, Teguh Citra; Diao, Caozheng; Yu, Xiaojiang; Breese, Mark B H; Venkatesan, T; Ariando; Rusydi, Andrivo

    2016-05-18

    Interfaces of two dissimilar complex oxides exhibit exotic physical properties that are absent in their parent compounds. Of particular interest is insulating LaAlO3 films on an insulating SrTiO3 substrate, where transport measurements have shown a metal-insulator transition as a function of LaAlO3 thickness. Their origin has become the subject of intense research, yet a unifying consensus remains elusive. Here, we report evidence for the electronic reconstruction in both insulating and conducting LaAlO3/SrTiO3 heterointerfaces revealed by O K-edge X-ray absorption spectroscopy. For the insulating samples, the O K-edge XAS spectrum exhibits features characteristic of electronically active point defects identified as noninteger valence states of Ti. For conducting samples, a new shape-resonance at ∼540.5 eV, characteristic of molecular-like oxygen (empty O-2p band), is observed. This implies that the concentration of electronic defects has increased in proportion with LaAlO3 thickness. For larger defect concentrations, the electronic defect states are no longer localized at the Ti orbitals and exhibit pronounced O 2p-O 2p character. Our results demonstrate that, above a critical thickness, the delocalization of O 2p electronic states can be linked to the presence of oxygen vacancies and is responsible for the enhancement of conductivity at the oxide heterointerfaces. PMID:27146607

  1. 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

  2. Local environment of Mn dopant in ZnO by near-edge x-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Kunisu, Masahiro; Oba, Fumiyasu; Ikeno, Hidekazu; Tanaka, Isao; Yamamoto, Tomoyuki

    2005-03-01

    High-resolution near-edge x-ray absorption fine structure (NEXAFS) at MnK edge is employed to probe the local environment of Mn dopant in ZnO. First-principles supercell calculations are systematically made to obtain theoretical NEXAFS. Mn is found to substitute for Zn up to 5at. %Mn in polycrystalline samples sintered at 1623K in air. Presence of Mn3O4 is apparent for samples with higher Mn content. The NEXAFS does not change in the range of Mn concentration from 0.01 to 5at.%, indicating the absence of Mn precipitates. The results are confirmed by examining the polarization dependence of the NEXAFS for a 5at.%-doped ZnO thin film.

  3. Micro-x-ray absorption near-edge structure imaging for detecting metallic Mn in GaN

    NASA Astrophysics Data System (ADS)

    Martínez-Criado, G.; Somogyi, A.; Homs, A.; Tucoulou, R.; Susini, J.

    2005-08-01

    In this study, we report the application of a synchrotron radiation microprobe to the analysis of Mn valencies in GaN. X-ray absorption near-edge structure (XANES) images taken around MnK-edge in fluorescence detection mode reveal the concentration of oxidation states of Mn centers. By fitting the XANES curve for each point of the image, the distributions of the Mn0, Mn2+, and Mn3+ oxidation states are obtained. At low Mn concentrations, there is a homogeneous mixture of Mn2+ and Mn3+ centers, while at high Mn content strong spatial-dependent Mn0 and Mn2+ distributions characterize the XANES maps. In a supplementary way with respect to Mn2+, the Mn0 pattern suggests the presence of specific cluster-like features, indicating surface segregation of metallic Mn centers.

  4. Edge effects on band gap energy in bilayer 2H-MoS{sub 2} under uniaxial strain

    SciTech Connect

    Dong, Liang; Wang, Jin; Dongare, Avinash M.; Namburu, Raju; O'Regan, Terrance P.; Dubey, Madan

    2015-06-28

    The potential of ultrathin MoS{sub 2} nanostructures for applications in electronic and optoelectronic devices requires a fundamental understanding in their electronic structure as a function of strain. Previous experimental and theoretical studies assume that an identical strain and/or stress state is always maintained in the top and bottom layers of a bilayer MoS{sub 2} film. In this study, a bilayer MoS{sub 2} supercell is constructed differently from the prototypical unit cell in order to investigate the layer-dependent electronic band gap energy in a bilayer MoS{sub 2} film under uniaxial mechanical deformations. The supercell contains an MoS{sub 2} bottom layer and a relatively narrower top layer (nanoribbon with free edges) as a simplified model to simulate the as-grown bilayer MoS{sub 2} flakes with free edges observed experimentally. Our results show that the two layers have different band gap energies under a tensile uniaxial strain, although they remain mutually interacting by van der Waals interactions. The deviation in their band gap energies grows from 0 to 0.42 eV as the uniaxial strain increases from 0% to 6% under both uniaxial strain and stress conditions. The deviation, however, disappears if a compressive uniaxial strain is applied. These results demonstrate that tensile uniaxial strains applied to bilayer MoS{sub 2} films can result in distinct band gap energies in the bilayer structures. Such variations need to be accounted for when analyzing strain effects on electronic properties of bilayer or multilayered 2D materials using experimental methods or in continuum models.

  5. Edge effects on band gap energy in bilayer 2H-MoS2 under uniaxial strain

    NASA Astrophysics Data System (ADS)

    Dong, Liang; Wang, Jin; Namburu, Raju; O'Regan, Terrance P.; Dubey, Madan; Dongare, Avinash M.

    2015-06-01

    The potential of ultrathin MoS2 nanostructures for applications in electronic and optoelectronic devices requires a fundamental understanding in their electronic structure as a function of strain. Previous experimental and theoretical studies assume that an identical strain and/or stress state is always maintained in the top and bottom layers of a bilayer MoS2 film. In this study, a bilayer MoS2 supercell is constructed differently from the prototypical unit cell in order to investigate the layer-dependent electronic band gap energy in a bilayer MoS2 film under uniaxial mechanical deformations. The supercell contains an MoS2 bottom layer and a relatively narrower top layer (nanoribbon with free edges) as a simplified model to simulate the as-grown bilayer MoS2 flakes with free edges observed experimentally. Our results show that the two layers have different band gap energies under a tensile uniaxial strain, although they remain mutually interacting by van der Waals interactions. The deviation in their band gap energies grows from 0 to 0.42 eV as the uniaxial strain increases from 0% to 6% under both uniaxial strain and stress conditions. The deviation, however, disappears if a compressive uniaxial strain is applied. These results demonstrate that tensile uniaxial strains applied to bilayer MoS2 films can result in distinct band gap energies in the bilayer structures. Such variations need to be accounted for when analyzing strain effects on electronic properties of bilayer or multilayered 2D materials using experimental methods or in continuum models.

  6. Erbium Doping Effects on the Conduction Band Edge in Germanium Nanocrystals

    SciTech Connect

    Meulenberg, Robert W.; Willey, Trevor M.; Lee, Jonathan R.; Terminello, Louis J.; Van Buren, T.

    2011-05-16

    We have produced erbium-doped germanium nanocrystals (NCs) using a new two cell physical vapor deposition system. Using element specific x-ray techniques (absorption and photoemission), we are able to probe the chemical environment of Er in the Ge NCs. Evidence for the optically active Er3+ state is seen at low Er concentrations, with a disruption of NC formation at high Er concentrations. The x-ray absorption measurements suggest that the Er occupies lattice sites near the surface of the NC. Analysis of the quantum confinement effect with Er doping suggests that the native quantum properties of the Ge NC are maintained at low Er concentrations.

  7. Conduction-band electronic states of YbInCu{sub 4} studied by photoemission and soft x-ray absorption spectroscopies

    SciTech Connect

    Utsumi, Yuki; Kurihara, Hidenao; Maso, Hiroyuki; Tobimatsu, Komei; Sato, Hitoshi; Shimada, Kenya; Namatame, Hirofumi; Hiraoka, Koichi; Kojima, Kenichi; Ohkochi, Takuo; Fujimori, Shin-ichi; Takeda, Yukiharu; Saitoh, Yuji; Mimura, Kojiro; Ueda, Shigenori; Yamashita, Yoshiyuki; Yoshikawa, Hideki; Kobayashi, Keisuke; Oguchi, Tamio; Taniguchi, Masaki

    2011-09-15

    We have studied conduction-band (CB) electronic states of a typical valence-transition compound YbInCu{sub 4} by means of temperature-dependent hard x-ray photoemission spectroscopy (HX-PES) of the Cu 2p{sub 3/2} and In 3d{sub 5/2} core states taken at h{nu}=5.95 keV, soft x-ray absorption spectroscopy (XAS) of the Cu 2p{sub 3/2} core absorption region around h{nu}{approx}935 eV, and soft x-ray photoemission spectroscopy (SX-PES) of the valence band at the Cu 2p{sub 3/2} absorption edge of h{nu}=933.0 eV. With decreasing temperature below the valence transition at T{sub V}=42 K, we have found that (1) the Cu 2p{sub 3/2} and In 3d{sub 5/2} peaks in the HX-PES spectra exhibit the energy shift toward the lower binding-energy side by {approx}40 and {approx}30 meV, respectively, (2) an energy position of the Cu 2p{sub 3/2} main absorption peak in the XAS spectrum is shifted toward higher photon-energy side by {approx}100 meV, with an appearance of a shoulder structure below the Cu 2p{sub 3/2} main absorption peak, and (3) an intensity of the Cu L{sub 3}VV Auger spectrum is abruptly enhanced. These experimental results suggest that the Fermi level of the CB-derived density of states is shifted toward the lower binding-energy side. We have described the valence transition in YbInCu{sub 4} in terms of the charge transfer from the CB to Yb 4f states.

  8. Anomalously Broad Diffuse Interstellar Bands and Excited CH+ Absorption in the Spectrum of Herschel 36

    NASA Astrophysics Data System (ADS)

    York, D. G.; Dahlstrom, J.; Welty, D. E.; Oka, T.; Hobbs, L. M.; Johnson, S.; Friedman, S. D.; Jiang, Z.; Rachford, B. L.; Snow, T. P.; Sherman, R.; Sonnentrucker, P.

    2014-02-01

    Anomalously broad diffuse interstellar bands (DIBs) at 5780.5, 5797.1, 6196.0, and 6613.6 Å are found in absorption along the line of sight to Herschel 36, an O star system next to the bright Hourglass nebula of the Hii region Messier 8. Excited lines of CH and CH+ are seen as well. We show that the region is very compact and itemize other anomalies of the gas. An infrared-bright star within 400 AU is noted. The combination of these effects produces anomalous DIBs, interpreted by Oka et al. (2013, see also this volume) as being caused predominantly by infrared pumping of rotational levels of relatively small molecules.

  9. 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.

  10. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    SciTech Connect

    Nelson, George J.; Harris, William M.; Izzo, John R. Jr.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu Yijin; Pianetta, Piero

    2011-04-25

    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.

  11. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    NASA Astrophysics Data System (ADS)

    Nelson, George J.; Harris, William M.; Izzo, John R.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu, Yijin; Pianetta, Piero

    2011-04-01

    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.

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

    DOE PAGESBeta

    Timoshenko, J.; Shivhare, A.; Scott, R. W.; Lu, D.; Frenkel, A. I.

    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.

  13. Final-State Projection Method in Charge-Transfer Multiplet Calculations: An Analysis of Ti L-Edge Absorption Spectra.

    PubMed

    Kroll, Thomas; Solomon, Edward I; de Groot, Frank M F

    2015-10-29

    A projection method to determine the final-state configuration character of all peaks in a charge transfer multiplet calculation of a 2p X-ray absorption spectrum is presented using a d(0) system as an example. The projection method is used to identify the most important influences on spectral shape and to map out the configuration weights. The spectral shape of a 2p X-ray absorption or L2,3-edge spectrum is largely determined by the ratio of the 2p core-hole interactions relative to the 2p3d atomic multiplet interaction. This leads to a nontrivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding. PMID:26226507

  14. 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.

  15. An asymmetric BODIPY triad with panchromatic absorption for high-performance red-edge laser emission.

    PubMed

    Duran-Sampedro, Gonzalo; Agarrabeitia, Antonia R; Garcia-Moreno, Inmaculada; Gartzia-Rivero, Leire; de la Moya, Santiago; Bañuelos, Jorge; López-Arbeloa, Íñigo; Ortiz, María J

    2015-07-21

    A rational design of an unprecedented asymmetric cassette triad based entirely on BODIPY chromophores allows efficient light harvesting over the UV-vis spectral region, leading to a bright and stable red-edge laser emission via efficient energy-transfer processes. PMID:26084606

  16. Development of Palladium L-Edge X-Ray Absorption Spectroscopy And Its Application for Chloropalladium Complexes

    SciTech Connect

    Boysen, R.B.; Szilagyi, R.K.

    2009-05-12

    X-ray absorption spectroscopy (XAS) is a synchrotron-based experimental technique that provides information about geometric and electronic structures of transition metal complexes. Combination of metal L-edge and ligand K-edge XAS has the potential to define the complete experimental ground state electronic structures for metal complexes with unoccupied d manifolds. We developed a quantitative treatment for Pd L-edge spectroscopy on the basis of the well-established chlorine K-edge XAS for a series of chloropalladium complexes that are pre-catalysts in various organic transformations. We found that Pd-Cl bonds are highly covalent, such as 24 {+-} 2%, 34 {+-} 3%, and 48 {+-} 4% chloride 3p character for each Pd-Cl bond in [PdCl{sub 4}]{sup 2-}, [PdCl{sub 6}]{sup 2-}, and PdCl{sub 2}, respectively. Pd(2p {yields} 4d) transition dipole integrals of 20.8 (SSRL)/16.9 (ALS) eV and 14.1 (SSRL)/11.9 (ALS) eV were determined using various combinations of L-edges for Pd(II) and Pd(IV), respectively. Application of metal-ligand covalency and transition dipole integrals were demonstrated for the example of bridging chloride ligands in PdCl{sub 2}. Our work lays the foundation for extending the quantitative treatment to other catalytically important ligands, such as phosphine, phosphite, olefin, amine, and alkyl in order to correlate the electronic structures of palladium complexes with their catalytic activity.

  17. Ultrafast carrier dynamics in band edge and broad deep defect emission ZnSe nanowires

    NASA Astrophysics Data System (ADS)

    Othonos, Andreas; Lioudakis, Emmanouil; Philipose, U.; Ruda, Harry E.

    2007-12-01

    Ultrafast carrier dynamics of ZnSe nanowires grown under different growth conditions have been studied. Transient absorption measurements reveal the dependence of the competing effects of state filling and photoinduced absorption on the probed energy states. The relaxation of the photogenerated carriers occupying defect states in the stoichiometric and Se-rich samples are single exponentials with time constants of 3-4ps. State filling is the main contribution for probe energies below 1.85eV in the Zn-rich grown sample. This ultrafast carrier dynamics study provides an important insight into the role that intrinsic point defects play in the observed photoluminescence from ZnSe nanowires.

  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

    NASA Astrophysics Data System (ADS)

    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. Self-absorption theory applied to rocket measurements of the nitric oxide (1, 0) gamma band in the daytime thermosphere

    NASA Technical Reports Server (NTRS)

    Eparvier, F. G.; Barth, C. A.

    1992-01-01

    Observations of the UV fluorescent emissions of the NO (1, 0) and (0, 1) gamma bands in the lower-thermospheric dayglow, made with a sounding rocket launched on March 7, 1989 from Poker Flat, Alaska, were analyzed. The resonant (1, 0) gamma band was found to be attenuated below an altitude of about 120 km. A self-absorption model based on Holstein transmission functions was developed for the resonant (1, 0) gamma band under varying conditions of slant column density and temperature and was applied for the conditions of the rocket flight. The results of the model agreed with the measured attenuation of the band, indicating the necessity of including self-absorption theory in the analysis of satellite and rocket limb data of NO.

  1. 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.

  2. 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

  3. Log spiral of revolution highly oriented pyrolytic graphite monochromator for fluorescence x-ray absorption edge fine structure

    SciTech Connect

    Pease, D. M.; Daniel, M.; Budnick, J. I.; Rhodes, T.; Hammes, M.; Potrepka, D. M.; Sills, K.; Nelson, C.; Heald, S. M.; Brewe, D. I.

    2000-09-01

    We have constructed an x-ray monochromator based on a log spiral of revolution covered with highly oriented pyrolytic graphite. Such a monochromator is used for obtaining x-ray absorption edge fine structure by the fluorescence method, and is particularly useful for measuring the fine structure of dilute element A in a concentrated matrix of element B, where B is to the left of A in the Periodic Table. Using the log spiral monochromator, we measure good Cr x-ray fine structure in an alloy of 1% Cr in a V matrix, whereas the corresponding spectrum is severely distorted by the V background if nonmonochromatized fluorescence is used. We also obtain excellent rejection of Mn fluorescence relative to Cr fluorescence in a Cr{sub 80}Mn{sub 20} alloy, and can tune the monochromator such that the entire Mn step height is significantly smaller than the Cr x-ray absorption edge fine structure oscillations for this system. (c) 2000 American Institute of Physics.

  4. 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.

  5. Angular Resolved X-Ray Absorption Near Edge Structure Investigation of Adsorbed Alkanethiol Monolayers on III-V(110) Surfaces

    NASA Astrophysics Data System (ADS)

    Chassé, T.; Zerulla, D.; Hallmeier, K. H.

    The structure of alkanethiol monolayers on III-V(110) surfaces was studied by analyzing the X-ray absorption near edge structure (XANES) of the carbon K edge. Pronounced absorption maxima were observed for special orientations of the polarization vector of the radiation as revealed from angular-dependent measurements, suggesting a rather well-defined molecular axis of the alkyl chains. From quantitative evaluations of these angular dependences the chains were found to be tilted from the normal towards the [001] direction of the (110) surfaces by 34° and 15° in the case of hexadecanethiol (HDT) adsorption on InP and GaP, respectively. The similarities as well as the differences in tilt angles between the substrates are dicussed in terms of constraints imposed by the surface structure and lattice constants as well as the space requirements of the van der Waals spheres of the adsorbed thiols. A unique feature observed on these monolayers is the nearly complete alignment of the alkyl chains with respect to the azimuthal orientation. We suggest that this adsorbate system represents the case of a single domain orientation within the organic monolayer.

  6. A passivated codoping approach to tailor the band edges of TiO{sub 2} for efficient photocatalytic degradation of organic pollutants

    SciTech Connect

    Wang Dan; Zou Yanhong; Wen Shuangchun; Fan Dianyuan

    2009-07-06

    We propose an effective passivated codoping approach to tailor the band edges of TiO{sub 2} by doping the host with group IVA and group VIB impurities to passive donor-acceptor complexes. A way of achieving p-type TiO{sub 2} is found, which can outspread the application range of TiO{sub 2} semiconductor. It is demonstrated that the carbon (C)/tungsten (W) codoped TiO{sub 2} has a substantial increase in the valence band edge, while leaving the conduction band edge almost unchanged, thus improving the efficiency of photocatalytic degradation of organic pollutants. In principle, the suggested approach for overcoming the p-type doping bottleneck can be applied to other wide-band-gap semiconductors.

  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. 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. PMID:24197060

  9. Tailoring growth conditions for efficient tuning of band edge of CdS nanoparticles

    SciTech Connect

    Susha, N.; Nair, Swapna S.; Aravind, P. B.; Anantharaman, M. R.

    2015-06-24

    CdS nanoparticles are successively synthesized by chemical precipitation method. The samples prepared at different reaction time and temperature are characterized by X-ray diffraction, Diffuse reflectance spectroscopy, Photoluminescence spectroscopy ans Energy dispersive x-ray analysis. Visible color variation is noted from light yellow to orange, indicates the quantum confinement effect and the results are again got confirmed from the optical studies. A shift in absorption peak is observed towards the lower region of the visible spectra - the “blue shift”- upon decrease in reaction time and temperature. Blue emission observed in the photoluminescence spectrum confirms the grain size induced confinement.

  10. 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.

  11. Retrieval of phytoplankton and colored detrital matter absorption coefficients with remote sensing reflectance in an ultraviolet band.

    PubMed

    Wei, Jianwei; Lee, Zhongping

    2015-02-01

    The light absorption of phytoplankton and colored detrital matter (CDM), which includes contribution of gelbstoff and detrital matters, has distinctive yet overlapping features in the ultraviolet (UV) and visible domain. The CDM absorption (a(dg)) increases exponentially with decreasing wavelength while the absorption coefficient of phytoplankton (a(ph)) generally decreases toward the shorter bands for the range of 350-450 nm. It has long been envisioned that including ocean color measurements in the UV range may help the separation of these two components from the remotely sensed ocean color spectrum. An attempt is made in this study to provide an analytical assessment of this expectation. We started with the development of an absorption decomposition model [quasi-analytical algorithm (QAA)-UV], analogous to the QAA, that partitions the total absorption coefficient using information at bands 380 and 440 nm. Compared to the retrieval results relying on the absorption information at 410 and 440 nm of the original QAA, our analyses indicate that QAA-UV can improve the retrieval of a(ph) and a(dg), although the improvement in accuracy is not significant for values at 440 nm. The performance of the UV-based algorithm is further evaluated with in situ measurements. The limited improvement observed with the field measurements highlights that the separation of a(dg) and a(ph) is highly dependent on the accuracy of the ocean color measurements and the estimated total absorption coefficient. PMID:25967770

  12. Dynamics of GaN band edge photoluminescence at near-room-temperature regime

    NASA Astrophysics Data System (ADS)

    Chen, Xiang-Bai; Huso, Jesse; Morrison, John L.; Bergman, Leah

    2006-02-01

    In this paper we present an approach based on the known radiative recombination rate model to study the dynamics and characteristics of photoluminescence (PL) transitions at room-temperature (RT) regime of GaN thin film. The model states that the dependence of the PL intensity on the laser excitation intensity is IPL~Ilaserα in which the value of the exponent α reveals whether the PL is due to an exciton or band gap recombination mechanism. We elaborated on the model and studied the temperature behavior of the exponent α in the range of 180-400 K in order to explore the recombination type for that range. It was found that at the temperature range just below RT ~180-270 K the exponent is a slowly increasing function of temperature and has an average value of ~1.2, implying a free-exciton recombination mechanism. At ~280 K the value of the exponent was found to exhibit a step-function-like behavior with a sharp increase from 1.2 to 1.7. At the temperature range just above RT ~300-400 K the exponent was found again to be a slowly increasing function of temperature with an average value of ~1.7, implying that at that temperature range the PL involves mainly band gap transitions. From the temperature behavior of the exponent, the activation energy of the free exciton was inferred to be ~24 meV.

  13. Influence of dye content on the conduction band edge of titania in the steam-treated dye-dispersing titania electrodes.

    PubMed

    Setiawan, Rudi Agus; Nishikiori, Hiromasa; Tanaka, Nobuaki; Fujii, Tsuneo

    2014-01-01

    The titania and dye-dispersing titania electrodes were prepared by a nitric acid-catalyzed sol-gel process. The dye-dispersing titania contains the dye molecules dispersed on the surface of the individual nanosized titania particles. The photo-cyclic voltammetry (Photo-CV) and photoelectric measurements of the dye-dispersing titania electrodes were conducted to clarify the factors changing the conduction band edge of the titania and the open-circuit voltage (Voc ) of the electrodes. The remaining nitrate ions caused a negative shift of conduction band edge of the titania of the dye-dispersing titania. The conduction band edge of the titania was shifted in a negative direction in the electrode containing a greater amount of the dye. These results are due to the adsorption of nitrate ions and the dye-titania complex formation on the titania particle surface. The effect of the dye-titania complex formation on the shift in the titania conduction band edge was greater than that of the adsorption of nitrate ions due to strong interaction between the dye and titania through the carboxylate and quinone-like groups of the dye. The shift in the titania conduction band edge corresponded to the change in the Voc value. PMID:24893823

  14. Lead uptake in diverse plant families: a study applying X-ray absorption near edge spectroscopy.

    PubMed

    Bovenkamp, Gudrun L; Prange, Alexander; Schumacher, Wolfgang; Ham, Kyungmin; Smith, Aaron P; Hormes, Josef

    2013-05-01

    The chemical environment of lead in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel Mountains in Germany was determined by Pb L3-edge XANES measurements using solid reference compounds and also aqueous solutions of different ionic strength simulating the plant environment. Pb(2+) ions in the plants were found to have two major coordinations, one with nine oxygen atoms in the first coordination shell similar to outer-sphere complexation and a second coordination with just three oxygen atoms similar to inner-sphere complexation. This can be interpreted assuming that lead is sorbed on the surface of cell walls depending on the concentration of lead in the soil solution. Pb L3-edge XANES spectra of dried and fresh plant samples are very similar because sorption does not change with removal of water but only because of the initial ionic strength. No bonding to biologically important groups (-S, - N) or precipitation (-PO4) was found. PMID:23517351

  15. Accurate measurements of ozone absorption cross-sections in the Hartley band

    NASA Astrophysics Data System (ADS)

    Viallon, J.; Lee, S.; Moussay, P.; Tworek, K.; Petersen, M.; Wielgosz, R. I.

    2015-03-01

    Ozone plays a crucial role in tropospheric chemistry, is the third largest contributor to greenhouse radiative forcing after carbon dioxide and methane and also a toxic air pollutant affecting human health and agriculture. Long-term measurements of tropospheric ozone have been performed globally for more than 30 years with UV photometers, all relying on the absorption of ozone at the 253.65 nm line of mercury. We have re-determined this cross-section and report a value of 11.27 x 10-18 cm2 molecule-1 with an expanded relative uncertainty of 0.86% (coverage factor k= 2). This is lower than the conventional value currently in use and measured by Hearn (1961) with a relative difference of 1.8%, with the consequence that historically reported ozone concentrations should be increased by 1.8%. In order to perform the new measurements of cross-sections with reduced uncertainties, a system was set up to generate pure ozone in the gas phase together with an optical system based on a UV laser with lines in the Hartley band, including accurate path length measurement of the absorption cell and a careful evaluation of possible impurities in the ozone sample by mass spectrometry and Fourier transform infrared spectroscopy. This resulted in new measurements of absolute values of ozone absorption cross-sections of 9.48 x 10-18, 10.44 x 10-18 and 11.07 x 10-18 cm2 molecule-1, with relative expanded uncertainties better than 0.7%, for the wavelengths (in vacuum) of 244.06, 248.32, and 257.34 nm respectively. The cross-section at the 253.65 nm line of mercury was determined by comparisons using a Standard Reference Photometer equipped with a mercury lamp as the light source. The newly reported value should be used in the future to obtain the most accurate measurements of ozone concentration, which are in closer agreement with non-UV-photometry based methods such as the gas phase titration of ozone with nitrogen monoxide.

  16. Annealing effect on the near-band edge emission of ZnO

    NASA Astrophysics Data System (ADS)

    Khomyak, V. V.; Slyotov, M. M.; Shtepliuk, I. I.; Lashkarev, G. V.; Slyotov, O. M.; Marianchuk, P. D.; Kosolovskiy, V. V.

    2013-02-01

    ZnO thin films have been grown on the sapphire (с-Al2O3) substrates at the temperature of 250 °C by means of the direct current (DC) magnetron sputtering technique. The crystal structure and surface morphology of the deposited films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The optical transmission, reflection and luminescence spectra at 300 K were analyzed for both the as-grown and post-annealed ZnO films. Using the λ-modulation method gives the possibility to reveal the main features of the energy band structure and the nature of the radiative transitions causing the ultraviolet (UV) luminescence.

  17. Nanopillar array band-edge laser cavities on silicon-on-insulator for monolithic integrated light sources

    NASA Astrophysics Data System (ADS)

    Lee, Wook-Jae; Kim, Hyunseok; Farrell, Alan C.; Senanayake, Pradeep; Huffaker, Diana L.

    2016-02-01

    A simple and unique laser scheme comprised of a finite-size nanopillar array on a silicon-on-insulator grating layer is introduced for realizing an on-chip monolithically integrated light source. A photonic band-edge mode, confined by the grating substrate in the vertical direction, shows a quality factor as high as 4000. We show that the proposed laser cavity allows direct coupling into a waveguide, which is essential for monolithic integration. In addition, III-V semiconductor nanopillars are grown on a silicon-on-insulator grating substrate in order to demonstrate the feasibility of epitaxy on 3D surfaces. These results provide a practical solution for on-chip integration of a monolithic light source.

  18. Mach bands and multiscale models of spatial vision: the role of first, second, and third derivative operators in encoding bars and edges.

    PubMed

    Wallis, Stuart A; Georgeson, Mark A

    2012-01-01

    Ernst Mach observed that light or dark bands could be seen at abrupt changes of luminance gradient in the absence of peaks or troughs in luminance. Many models of feature detection share the idea that bars, lines, and Mach bands are found at peaks and troughs in the output of even-symmetric spatial filters. Our experiments assessed the appearance of Mach bands (position and width) and the probability of seeing them on a novel set of generalized Gaussian edges. Mach band probability was mainly determined by the shape of the luminance profile and increased with the sharpness of its corners, controlled by a single parameter (n). Doubling or halving the size of the images had no significant effect. Variations in contrast (20%-80%) and duration (50-300 ms) had relatively minor effects. These results rule out the idea that Mach bands depend simply on the amplitude of the second derivative, but a multiscale model, based on Gaussian-smoothed first- and second-derivative filtering, can account accurately for the probability and perceived spatial layout of the bands. A key idea is that Mach band visibility depends on the ratio of second- to first-derivative responses at peaks in the second-derivative scale-space map. This ratio is approximately scale-invariant and increases with the sharpness of the corners of the luminance ramp, as observed. The edges of Mach bands pose a surprisingly difficult challenge for models of edge detection, but a nonlinear third-derivative operation is shown to predict the locations of Mach band edges strikingly well. Mach bands thus shed new light on the role of multiscale filtering systems in feature coding. PMID:23262150

  19. Two-photon absorption cross section measurement in the gamma band system of nitric oxide

    SciTech Connect

    Burris, J.F. Jr.

    1982-01-01

    A dye laser with a single longitudinal mode and very stable spatial mode structure has been constructed. With this laser system a four-wave mixing experiment was done in the gamma bands of nitric oxide using two photon resonance. Another four-wave mixing experiment was done in nitrogen using coherent anti-Stokes Raman scattering (CARS) and the two signals ratioed. Using accurately known values of the Raman scattering cross section, the third order susceptibility in NO was determined without needing to know the spatial and temporal properties of the dye lasers. From this susceptibility, the two photon absorption cross section was calculated with the explicit dependence of sigma/sup (2)/ upon X/sup (3)/ shown. For the R/sub 22/ + S/sub 12/(J'' = 9 1/2) (A/sup 2/..sigma..+(v' = 0) -- X/sup 2/..pi..(v'' = 0)) line, sigma/sup (2)/ = (1.0 +/- 0.6) x 10/sup -38/cm/sup 4/g(2/sub 1/-Vertical Barsub f/ is the normalized lineshape. Branching ratios for the A/sup 2/..sigma..+(v' = n) ..-->.. X/sup 2/..omega..(v'' = n)(n = o,...9) transitions of NO were also measured, Franck-Condon factors calculated and the lifetime of the A state determined.

  20. Absolute radical densities in etching plasmas determined by broad-band UV absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Booth, Jean-Paul; Cunge, Gilles; Neuilly, François; Sadeghi, Nader

    1998-08-01

    Broad-band UV absorption spectroscopy was used to determine radical densities in reactive gas plasmas generated in a 13.56 MHz capacitively coupled parallel plate reactor. Five radical species were detected: 0963-0252/7/3/021/img1, CF, AlF, 0963-0252/7/3/021/img2 and 0963-0252/7/3/021/img3. Absolute (line-integrated) 0963-0252/7/3/021/img1 densities were determined in 0963-0252/7/3/021/img5 and 0963-0252/7/3/021/img6 plasmas, as were the 0963-0252/7/3/021/img1 vibrational and rotational temperatures in the latter case. In 0963-0252/7/3/021/img5 plasmas the CF radical was also detected, along with the etch products AlF (from the Al powered electrode) and 0963-0252/7/3/021/img2 (when an Si substrate was present). The fraction that 0963-0252/7/3/021/img2 comprises of the total etch products was estimated. Finally, the 0963-0252/7/3/021/img3 dimer was detected in an 0963-0252/7/3/021/img12 plasma in the presence of an Si substrate. This simple technique allows absolute concentrations of many key reactive species to be determined in reactive plasmas, without the need to analyse the complex rotational spectra of these polyatomic molecules.

  1. Band gap tuning and optical absorption in type-II InAs/GaSb mid infrared short period superlattices: 14 bands K Dot-Operator p study

    SciTech Connect

    AbuEl-Rub, Khaled M.

    2012-09-06

    The MBE growth of short-period InAs/GaSb type-II superlattice structures, varied around 20.5 A InAs/24 A GaSb were [J. Applied physics, 96, 2580 (2004)] carried out by Haugan et al. These SLs were designed to produce devices with an optimum mid-infrared photoresponse and a sharpest photoresponse cutoff. We have used a realistic and reliable 14-band k.p formalism description of the superlattice electronic band structure to calculate the absorption coefficient in such short-period InAs/GaSb type-II superlattices. The parameters for this formalism are known from fitting to independent experiments for the bulk materials. The band-gap energies are obtained without any fitting parameters, and are in good agreement with experimental data.

  2. Visualizing band offsets and edge states in bilayer-monolayer transition metal dichalcogenides lateral heterojunction.

    PubMed

    Zhang, Chendong; Chen, Yuxuan; Huang, Jing-Kai; Wu, Xianxin; Li, Lain-Jong; Yao, Wang; Tersoff, Jerry; Shih, Chih-Kang

    2016-01-01

    Semiconductor heterostructures are fundamental building blocks for many important device applications. The emergence of two-dimensional semiconductors opens up a new realm for creating heterostructures. As the bandgaps of transition metal dichalcogenides thin films have sensitive layer dependence, it is natural to create lateral heterojunctions (HJs) using the same materials with different thicknesses. Here we show the real space image of electronic structures across the bilayer-monolayer interface in MoSe2 and WSe2, using scanning tunnelling microscopy and spectroscopy. Most bilayer-monolayer HJs are found to have a zig-zag-orientated interface, and the band alignment of such atomically sharp HJs is of type-I with a well-defined interface mode that acts as a narrower-gap quantum wire. The ability to utilize such commonly existing thickness terraces as lateral HJs is a crucial addition to the tool set for device applications based on atomically thin transition metal dichalcogenides, with the advantage of easy and flexible implementation. PMID:26778119

  3. Visualizing band offsets and edge states in bilayer-monolayer transition metal dichalcogenides lateral heterojunction

    NASA Astrophysics Data System (ADS)

    Zhang, Chendong; Chen, Yuxuan; Huang, Jing-Kai; Wu, Xianxin; Li, Lain-Jong; Yao, Wang; Tersoff, Jerry; Shih, Chih-Kang

    2016-01-01

    Semiconductor heterostructures are fundamental building blocks for many important device applications. The emergence of two-dimensional semiconductors opens up a new realm for creating heterostructures. As the bandgaps of transition metal dichalcogenides thin films have sensitive layer dependence, it is natural to create lateral heterojunctions (HJs) using the same materials with different thicknesses. Here we show the real space image of electronic structures across the bilayer-monolayer interface in MoSe2 and WSe2, using scanning tunnelling microscopy and spectroscopy. Most bilayer-monolayer HJs are found to have a zig-zag-orientated interface, and the band alignment of such atomically sharp HJs is of type-I with a well-defined interface mode that acts as a narrower-gap quantum wire. The ability to utilize such commonly existing thickness terraces as lateral HJs is a crucial addition to the tool set for device applications based on atomically thin transition metal dichalcogenides, with the advantage of easy and flexible implementation.

  4. Visualizing band offsets and edge states in bilayer–monolayer transition metal dichalcogenides lateral heterojunction

    PubMed Central

    Zhang, Chendong; Chen, Yuxuan; Huang, Jing-Kai; Wu, Xianxin; Li, Lain-Jong; Yao, Wang; Tersoff, Jerry; Shih, Chih-Kang

    2016-01-01

    Semiconductor heterostructures are fundamental building blocks for many important device applications. The emergence of two-dimensional semiconductors opens up a new realm for creating heterostructures. As the bandgaps of transition metal dichalcogenides thin films have sensitive layer dependence, it is natural to create lateral heterojunctions (HJs) using the same materials with different thicknesses. Here we show the real space image of electronic structures across the bilayer–monolayer interface in MoSe2 and WSe2, using scanning tunnelling microscopy and spectroscopy. Most bilayer–monolayer HJs are found to have a zig-zag-orientated interface, and the band alignment of such atomically sharp HJs is of type-I with a well-defined interface mode that acts as a narrower-gap quantum wire. The ability to utilize such commonly existing thickness terraces as lateral HJs is a crucial addition to the tool set for device applications based on atomically thin transition metal dichalcogenides, with the advantage of easy and flexible implementation. PMID:26778119

  5. Vegetation Red-edge Spectral Modeling for Solar-induced Chlorophyll Fluorescence Retrieval at O2-B Band

    NASA Astrophysics Data System (ADS)

    Huang, C.; Zhang, L.; Qiao, N.; Zhang, X.; Li, Y.

    2015-12-01

    Remotely sensed solar-induced chlorophyll fluorescence (SIF) has been considered an ideal probe in monitoring global vegetation photosynthesis. However, challenges in accurate estimate of faint SIF (less than 5% of the total reflected radiation in near infrared bands) from the observed apparent reflected radiation greatly limit its wide applications. Currently, the telluric O2-B (~688nm) and O2-A (~761nm) have been proved to be capable of SIF retrieval based on Fraunhofer line depth (FLD) principle. They may still work well even using conventional ground-based commercial spectrometers with typical spectral resolutions of 2~5 nm and high enough signal-to-noise ratio (e.g., the ASD spectrometer). Nevertheless, almost all current FLD based algorithms were mainly developed for O2-A, a few concentrating on the other SIF emission peak in O2-B. One of the critical reasons is that it is very difficult to model the sudden varying reflectance around O2-B band located in the red-edge spectral region (about 680-800 nm). This study investigates a new method by combining the established inverted Gaussian reflectance model (IGM) and FLD principle using diurnal canopy spectra with relative low spectral resolutions of 1 nm (FluorMOD simulations) and 3 nm (measured by ASD spectrometer) respectively. The IGM has been reported to be an objective and good method to characterize the entire vegetation red-edge reflectance. Consequently, the proposed SIF retrieval method (hereinafter called IGMFLD) could exploit all the spectral information along the whole red-edge (680-800 nm) to obtain more reasonable reflectance and fluorescence correction coefficients than traditional FLD methods such as the iFLD. Initial results show that the IGMFLD can better capture the spectrally non-linear characterization of the reflectance in 680-800 nm and thereby yields much more accurate SIFs in O2-B than typical FLD methods, including sFLD, 3FLD and iFLD (see figure 1). Finally, uncertainties and prospect

  6. Band edge emission enhancement by quadrupole surface plasmon-exciton coupling using direct-contact Ag/ZnO nanospheres.

    PubMed

    Zang, Yashu; He, Xu; Li, Jing; Yin, Jun; Li, Kongyi; Yue, Chuang; Wu, Zhiming; Wu, Suntao; Kang, Junyong

    2013-01-21

    Periodic Ag nanoball (NB) arrays on ZnO hollow nanosphere (HNS) supporting structures were fabricated in a large area by a laser irradiation method. The optimized laser power and spherical supporting structure of ZnO with a certain size and separation were employed to aggregate a sputtering-deposited Ag nano-film into an ordered, large-area, and two dimensional Ag NB array. A significant band edge (BE) emission enhancement of ZnO HNSs was achieved on this Ag NB/ZnO HNS hybrid structure and the mechanism was revealed by further experimental and theoretical analyses. With successfully fabricating the direct-contact structure of a Ag NB on the top of each ZnO HNS, the highly localized quadrupole mode surface plasmon resonance (SPR), realized on the metal NBs in the ultraviolet region, can effectively improve the BE emission of ZnO through strong coupling with the excitons of ZnO. Compared with the dipole mode SPR, the quadrupole mode SPR is insensitive to the metal nanoparticle's size and has a resonance frequency in the BE region of the wide band gap materials, hence, it can be potentially applied in related optoelectronic devices. PMID:23196786

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

    SciTech Connect

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

    2015-07-15

    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.

  8. 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.

  9. 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.

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

    SciTech Connect

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

    2012-04-14

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

  11. 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.

  12. Extremely asymmetric diffraction as a method of determining magneto-optical constants for X-rays near absorption edges

    NASA Astrophysics Data System (ADS)

    Andreeva, M. A.; Repchenko, Yu. L.; Smekhova, A. G.; Dumesnil, K.; Wilhelm, F.; Rogalev, A.

    2015-06-01

    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 3 absorption edge of yttrium in a single-crystal YFe2 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)/YFe2(40 nm<110>)/Fe(1.5 nm)/Nb(50 nm)/sapphire sample at the European Synchrotron Radiation Facility has been made.

  13. Tracking Drug Loading Capacities of Calcium Silicate Hydrate Carrier: A Comparative X-ray Absorption Near Edge Structures Study.

    PubMed

    Guo, Xiaoxuan; Wang, Zhiqiang; Wu, Jin; Yiu, Yun-Mui; Hu, Yongfeng; Zhu, Ying-Jie; Sham, Tsun-Kong

    2015-08-01

    Mesoporous spheres of calcium silicate hydrate (MS-CSH) have been prepared by an ultrasonic method. Following an earlier work in which we have revealed the interactions between ibuprofen (IBU) and CSH carriers with different morphologies by X-ray absorption near edge structures (XANES) analysis. In the present investigation, two new drug molecules, alendronate sodium (ALN) and gentamicin sulfate (GS), were incorporated into MS-CSH, and their drug loading capacities (DLCs) were measured using thermogravimetric analysis to establish the relationship between drug-carrier interactions and DLCs. The XANES spectra clearly indicate that acidic functional groups of the drug molecules linked to the active sites (Ca-OH and Si-OH groups) of MS-CSH on the surface by electrostatic interactions. In addition, it is found that the stoichiometric ratio of Ca(2+) ions of CSH carriers and the functional groups of drug molecules may significantly influence the DLCs. PMID:26162602

  14. Anisotropy of Chemical Bonds in Collagen Molecules Studied by X-ray Absorption Near-Edge Structure (XANES) Spectroscopy

    PubMed Central

    Lam, Raymond S.K.; Metzler, Rebecca A.; Gilbert, Pupa U.P.A.; Beniash, Elia

    2012-01-01

    Collagen type I fibrils are the major building blocks of connective tissues. Collagen fibrils are anisotropic supra-molecular 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. PMID:22148847

  15. Structural diversity of the 3-micron absorption band in Enceladus’ plume from Cassini VIMS: Insights into subsurface environmental conditions

    NASA Astrophysics Data System (ADS)

    Dhingra, Deepak; Hedman, Matthew M.; Clark, Roger N.

    2015-11-01

    Water ice particles in Enceladus’ plume display their diagnostic 3-micron absorption band in Cassini VIMS data. These near infrared measurements of the plume also exhibit noticeable variations in the character of this band. Mie theory calculations reveal that the shape and location of the 3-micron band are controlled by a number of environmental and structural parameters. Hence, this band provides important insights into the properties of the water ice grains and about the subsurface environmental conditions under which they formed. For example, the position of the 3-micron absorption band minimum can be used to distinguish between crystalline and amorphous forms of water ice and to constrain the formation temperature of the ice grains. VIMS data indicates that the water ice grains in the plume are dominantly crystalline which could indicate formation temperatures above 113 K [e.g. 1, 2]. However, there are slight (but observable) variations in the band minimum position and band shape that may hint at the possibility of varying abundance of amorphous ice particles within the plume. The modeling results further indicate that there are systematic shifts in band minimum position with temperature for any given form of ice but the crystalline and amorphous forms of water ice are still distinguishable at VIMS spectral resolution. Analysis of the eruptions from individual source fissures (tiger stripes) using selected VIMS observations reveal differences in the 3-micron band shape that may reflect differences in the size distributions of the water ice particles along individual fissures. Mie theory models suggest that big ice particles (>3 micron) may be an important component of the plume.[1] Kouchi, A., T. Yamamoto, T. Kozasa, T. Kuroda, and J. M. Greenberg (1994) A&A, 290, 1009-1018 [2] Mastrapa, R. M. E., W. M. Grundy, and M. S. Gudipati (2013) in M. S. Gudipati and J. Castillo-Rogez (Eds.), The Science of Solar System Ices, pp. 371.

  16. X-ray absorption, glancing-angle reflectivity, and theoretical study of the N K- and Ga M{sub 2,3}-edge spectra in GaN

    SciTech Connect

    Lambrecht, W.R.; Rashkeev, S.N.; Segall, B.; Lawniczak-Jablonska, K.; Suski, T.; Gullikson, E.M.; Underwood, J.H.; Perera, R.C.; Rife, J.C.; Grzegory, I.; Porowski, S.; Wickenden, D.K.

    1997-01-01

    A comprehensive study of the nitrogen K edge and gallium M{sub 2,3} edge in gallium nitride is presented. Results of two different experimental techniques, x-ray absorption by total photocurrent measurements and glancing-angle x-ray reflectivity, are compared with each other. First-principles calculations of the (polarization averaged) dielectric response {epsilon}{sub 2}({omega}) contributions from the relevant core-level to conduction-band transitions and derived spectral functions are used to interpret the data. These calculations are based on the local density approximation (LDA) and use a muffin-tin orbital basis for the band structure and matrix elements. The angular dependence of the x-ray reflectivity is studied and shown to be in good agreement with the theoretical predictions based on Fresnel theory and the magnitude of the calculated x-ray optical response functions. The main peaks in the calculated and measured spectra are compared with those in the relevant partial density of conduction-band states. Assignments are made to particular band transitions and corrections to the LDA are discussed. From the analysis of the N K and Ga M{sub 2,3} edges the latter are found to be essentially constant up to {approximately}10 eV above the conduction-band minimum. The differences in spectral shape found between the various measurements were shown to be a result of polarization dependence. Since the c axis in all the measurements was normal to the sample surface, p-polarized radiation at glancing angles corresponds to {bold E}{parallel}{bold c} while s polarization corresponds to {bold E}{perpendicular}{bold c} at all incident angles. Thus, this polarization dependence is a result of the intrinsic anisotropy of the wurtzite structure. Spectra on powders which provide an average of both polarizations as well as separate measurements of reflectivity with s polarization and p polarization were used. {copyright} {ital 1997} {ital The American Physical Society}

  17. Evidence of a Shockley-Read-Hall Defect State Independent of Band-Edge Energy in InAs /In (As ,Sb ) Type-II Superlattices

    NASA Astrophysics Data System (ADS)

    Aytac, Y.; Olson, B. V.; Kim, J. K.; Shaner, E. A.; Hawkins, S. D.; Klem, J. F.; Flatté, M. E.; Boggess, T. F.

    2016-05-01

    A set of seven InAs /In (As ,Sb ) type-II superlattices (T2SLs) are designed to have specific band-gap energies between 290 meV (4.3 μ m ) and 135 meV (9.2 μ m ) in order to study the effects of the T2SL band-gap energy on the minority-carrier lifetime. A temperature-dependent optical pump-probe technique is used to measure the carrier lifetimes, and the effect of a midgap defect level on the carrier-recombination dynamics is reported. The Shockley-Read-Hall (SRH) defect state is found to be at energy of approximately -250 ±12 meV relative to the valence-band edge of bulk GaSb for the entire set of T2SL structures, even though the T2SL valence-band edge shifts by 155 meV on the same scale. These results indicate that the SRH defect state in InAs /In (As ,Sb ) T2SLs is singular and is nearly independent of the exact position of the T2SL band-gap or band-edge energies. They also suggest the possibility of engineering the T2SL structure such that the SRH state is removed completely from the band gap, a result that should significantly increase the minority-carrier lifetime.

  18. 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.

  19. Ligand and Charge Dependence for Absorption Edge in XANES Spectra of TPP[Fe(Pc)L2]2 Systems

    NASA Astrophysics Data System (ADS)

    Takahashi, Kei; Watanabe, Akie; Niki, Kaori; Hanasaki, Noriaki; Kanda, Akinori; Fujikawa, Takashi

    We apply real space full multiple scattering theory to interpret the Fe K-edge XANES spectra of TPP[Fe(Pc)L2]2 (L = CN, Cl and Br) systems, which show the giant magnetoresistance (GMR) at the low temperatures. In the previous paper, we have reported the absorption edge shift of the XANES spectra, whose origin remains unclear, for TPP[Fe(Pc)L2]2 systems. In order to clarify the relation between the charge of the Fe atom, the local structure of the axial ligand and the XANES spectra, we improve the calculation of the XANES spectra by taking into account the wider region including the neighboring Fe(Pc)L2 and TPP molecules. Our multiple scattering analyses suggest that the spectral shape is strongly influenced by the distance between a central Fe and axial ligands L. The number of Fe 3d electrons obtained by density functional theory calculations show weak dependence on the axial ligands L. The EXAFS spectra, the polarization dependence and the temperature dependence of the XANES spectra are also discussed.

  20. Near-edge X-ray absorption fine-structure spectroscopy of naphthalene diimide-thiophene co-polymers

    SciTech Connect

    Gann, Eliot; McNeill, Christopher R.; Szumilo, Monika; Sirringhaus, Henning; Sommer, Michael; Maniam, Subashani; Langford, Steven J.; Thomsen, Lars

    2014-04-28

    Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy is an important tool for probing the structure of conjugated polymer films used in organic electronic devices. High-performance conjugated polymers are often donor-acceptor co-polymers which feature a repeat unit with multiple functional groups. To facilitate better application of NEXAFS spectroscopy to the study of such materials, improved understanding of the observed NEXAFS spectral features is required. In order to examine how the NEXAFS spectrum of a donor-acceptor co-polymer relates to the properties of the sub-units, a series of naphthalene diimide-thiophene-based co-polymers have been studied where the nature and length of the donor co-monomer has been systematically varied. The spectra of these materials are compared with that of a thiophene homopolymer and naphthalene diimide monomer enabling peak assignment and the influence of inter-unit electronic coupling to be assessed. We find that while it is possible to attribute peaks within the π* manifold as arising primarily due to the naphthalene diimide or thiophene sub-units, very similar dichroism of these peaks is observed indicating that it may not be possible to separately probe the molecular orientation of the separate sub-units with carbon K-edge NEXAFS spectroscopy.

  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. PMID:26253227

  2. Enhancement of the near-band-edge photoluminescence of ZnO nanowires: Important role of hydrogen incorporation versus plasmon resonances

    SciTech Connect

    Dev, A.; Richters, J. P.; Gutowski, J.; Voss, T.; Sartor, J.; Kalt, H.

    2011-03-28

    We investigated the photoluminescence properties of ZnO nanowires coated with Au, Ag, and Pt nanoparticles deposited by dc sputtering. A strong enhancement of the near-band-edge emission was observed in all metal-coated samples but also if the samples were treated with Ar plasma without any nanoparticle deposition. High-resolution photoluminescence spectroscopy revealed hydrogen-donor-bound-exciton emission in all samples indicating unintentional hydrogen incorporation. A shorter decay time of the near-band-edge emission was observed in all cases. The results indicate that unintentional hydrogen incorporation plays a dominant role when metal deposition is performed by sputtering.

  3. Airborne imaging spectrometer data of the Ruby Mountains, Montana: Mineral discrimination using relative absorption band-depth images

    USGS Publications Warehouse

    Crowley, J.K.; Brickey, D.W.; Rowan, L.C.

    1989-01-01

    Airborne imaging spectrometer data collected in the near-infrared (1.2-2.4 ??m) wavelength range were used to study the spectral expression of metamorphic minerals and rocks in the Ruby Mountains of southwestern Montana. The data were analyzed by using a new data enhancement procedure-the construction of relative absorption band-depth (RBD) images. RBD images, like bandratio images, are designed to detect diagnostic mineral absorption features, while minimizing reflectance variations related to topographic slope and albedo differences. To produce an RBD image, several data channels near an absorption band shoulder are summed and then divided by the sum of several channels located near the band minimum. RBD images are both highly specific and sensitive to the presence of particular mineral absorption features. Further, the technique does not distort or subdue spectral features as sometimes occurs when using other data normalization methods. By using RBD images, a number of rock and soil units were distinguished in the Ruby Mountains including weathered quartz - feldspar pegmatites, marbles of several compositions, and soils developed over poorly exposed mica schists. The RBD technique is especially well suited for detecting weak near-infrared spectral features produced by soils, which may permit improved mapping of subtle lithologic and structural details in semiarid terrains. The observation of soils rich in talc, an important industrial commodity in the study area, also indicates that RBD images may be useful for mineral exploration. ?? 1989.

  4. Depth and Shape of the 0.94-microm Water Vapor Absorption Band for Clear and Cloudy Skies.

    PubMed

    Volz, F E

    1969-11-01

    Sky radiation near zenith and solar radiation in the rhosigmatau band region were recorded by means of a rotating interference filter (lambda0.98-0.88 microm) and a silicon detector. Although the spectral resolution of the simple spectrometer was not high, the water vapor content of the cloud free atmosphere was obtained with reasonable accuracy. The band depth of the radiation from thin, bright clouds was only slightly greater than that of the cloud free atmosphere, but dense and dark clouds showed deep bands mainly caused by increased path length as a result of multiple scattering. Considerable distortion of the band due to absorption by liquid water is observed in the radiation from very dark and dense clouds, and sometimes during snowfall. Some laboratory measurements are also discussed. PMID:20076009

  5. X-ray absorption near edge spectroscopy with a superconducting detector for nitrogen dopants in SiC

    PubMed Central

    Ohkubo, M.; Shiki, S.; Ukibe, M.; Matsubayashi, N.; Kitajima, Y.; Nagamachi, S.

    2012-01-01

    Fluorescence-yield X-ray absorption fine structure (FY-XAFS) is extensively used for investigating atomic-scale local structures around specific elements in functional materials. However, conventional FY-XAFS instruments frequently cannot cover trace light elements, for example dopants in wide gap semiconductors, because of insufficient energy resolution of semiconductor X-ray detectors. Here we introduce a superconducting XAFS (SC-XAFS) apparatus to measure X-ray absorption near-edge structure (XANES) of n-type dopant N atoms (4 ×1019 cm−3) implanted at 500°C into 4H-SiC substrates annealed subsequently. The XANES spectra and ab initio multiple scattering calculations indicate that the N atoms almost completely substitute for the C sites, associated with a possible existence of local CN regions, in the as-implanted state. This is a reason why hot implantation is necessary for dopant activation in ion implantation. The SC-XAFS apparatus may play an important role in improving doping processes for energy-saving wide-gap semiconductors and other functional materials. PMID:23152937

  6. X-ray phase-amplitude contrast mapping of single-crystal alloys near the absorption edge of the alloy impurity

    NASA Astrophysics Data System (ADS)

    Nikulin, A. Yu.; Davis, J. R.; Jones, N. T.; Zaumseil, P.

    1998-11-01

    An experimental-analytical method for the nondestructive structural and chemical composition mapping of single-crystal alloys is proposed, implemented, and successfully tested. The technique is based on analytical measurements of phase and amplitude changes in a narrow polychromatic region near the absorption edge of the alloy impurity. Synchrotron radiation energies of 11.096-11.105 keV were used to measure the Bragg diffraction profiles near the absorption edge of germanium at 11.103 keV in SiGe/Si crystal alloy superstructures. Physical dimensions and chemical composition of SiGe alloys were determined with a spatial resolution 8.6 Å.

  7. Evidence for strange stars from joint observation of harmonic absorption bands and of redshift

    NASA Astrophysics Data System (ADS)

    Bagchi, Manjari; Ray, Subharthi; Dey, Mira; Dey, Jishnu

    2006-05-01

    From recent reports on terrestrial heavy ion collision experiments it appears that one may not obtain information about the existence of asymptotic freedom (AF) and chiral symmetry restoration (CSR) for quarks of QCD at high density. This information may still be obtained from compact stars - if they are made up of strange quark matter (SQM). Very high gravitational redshift lines (GRL), seen from some compact stars, seem to suggest high ratios of mass and radius (M/R) for them. This is suggestive of strange stars (SS) and can in fact be fitted very well with SQM equation of state (EOS) deduced with built in AF and CSR. In some other stars broad absorption bands (BAB) appear at about ~0.3keV and multiples thereof, that may fit in very well with resonance with harmonic compressional breathing mode frequencies of these SS. Emission at these frequencies are also observed in six stars. If these two features of large GRL and BAB were observed together in a single star, it would strengthen the possibility for the existence of SS in nature and would vindicate the current dogma of AF and CSR that we believe in QCD. Recently, in 4U 1700 - 24, both features appear to be detected, which may well be interpreted as observation of SS - although the group that analyzed the data did not observe this possibility. We predict that if the shifted lines, that has been observed, are from neon with GRL shift z= 0.4- then the compact object emitting it is a SS of mass 1.2Msolar and radius 7km. In addition the fit to the spectrum leaves a residual with broad dips at 0.35keV and multiples thereof, as in 1E 1207 - 5209 which is again suggestive of SS.

  8. Mapping atomic and diffuse interstellar band absorption across the Magellanic Clouds and the Milky Way

    NASA Astrophysics Data System (ADS)

    Bailey, Mandy; van Loon, Jacco Th.; Sarre, Peter J.; Beckman, John E.

    2015-12-01

    Diffuse interstellar bands (DIBs) trace warm neutral and weakly ionized diffuse interstellar medium (ISM). Here we present a dedicated, high signal-to-noise spectroscopic survey of two of the strongest DIBs, at 5780 and 5797 Å, in optical spectra of 666 early-type stars in the Small and Large Magellanic Clouds, along with measurements of the atomic Na I D and Ca II K lines. The resulting maps show for the first time the distribution of DIB carriers across large swathes of galaxies, as well as the foreground Milky Way ISM. We confirm the association of the 5797 Å DIB with neutral gas, and the 5780 Å DIB with more translucent gas, generally tracing the star-forming regions within the Magellanic Clouds. Likewise, the Na I D line traces the denser ISM whereas the Ca II K line traces the more diffuse, warmer gas. The Ca II K line has an additional component at ˜200-220 km s-1 seen towards both Magellanic Clouds; this may be associated with a pan-Magellanic halo. Both the atomic lines and DIBs show sub-pc-scale structure in the Galactic foreground absorption; the 5780 and 5797 Å DIBs show very little correlation on these small scales, as do the Ca II K and Na I D lines. This suggests that good correlations between the 5780 and 5797 Å DIBs, or between Ca II K and Na I D, arise from the superposition of multiple interstellar structures. Similarity in behaviour between DIBs and Na I in the Small Magellanic Cloud (SMC), Large Magellanic Cloud (LMC) and Milky Way suggests the abundance of DIB carriers scales in proportion to metallicity.

  9. 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.

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

    PubMed

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

    2014-06-28

    S K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT) calculations were performed on a series of As[S2CNR2]3 complexes, where R2 = Et2, (CH2)5 and Ph2, to determine how dithiocarbamate substituents attached to N affect As[S2CNR2]3 electronic structure. Complimentary [PPh4][S2CNR2] salts were also studied to compare dithiocarbamate bonding in the absence of As. The XAS results indicate that changing the orientation of the alkyl substituents from trans to cis (R2 = Et2vs. (CH2)5) yields subtle variations whereas differences associated with a change from alkyl to aryl are much more pronounced. For example, despite the differences in As 4p mixing, the first features in the S K-edge XAS spectra of [PPh4][S2CNPh2] and As[S2CNPh2]3 were both shifted by 0.3 eV compared to their alkyl-substituted derivatives. DFT calculations revealed that the unique shift observed for [PPh4][S2CNPh2] is due to phenyl-induced splitting of the π* orbitals delocalized over N, C and S. A similar phenomenon accounts for the shift observed for As[S2CNPh2]3, but the presence of two unique S environments (As-S and As···S) prevented reliable analysis of As-S covalency from the XAS data. In the absence of experimental values, DFT calculations revealed a decrease in As-S orbital mixing in As[S2CNPh2]3 that stems from a redistribution of electron density to S atoms participating in weaker As···S interactions. Simulated spectra obtained from TDDFT calculations reproduce the experimental differences in the S K-edge XAS data, which suggests that the theory is accurately modeling the experimental differences in As-S orbital mixing. The results highlight how S K-edge XAS and DFT can be used cooperatively to understand the electronic structure of low symmetry coordination complexes containing S atoms in different chemical environments. PMID:24811926

  12. The absorption coefficient of the liquid N2 2.15-micron band and application to Triton

    NASA Technical Reports Server (NTRS)

    Grundy, William M.; Fink, Uwe

    1991-01-01

    The present measurements of the temperature dependence exhibited by the liquid N2 2.15-micron 2-0 collision-induced band's absorption coefficient and integrated absorption show the latter to be smaller than that of the N2 gas, and to decrease with decreasing temperature. Extrapolating this behavior to Triton's nominal surface temperature yields a new estimate of the N2-ice grain size on the Triton south polar cap; a mean N2 grain size of 0.7-3.0 cm is consistent with grain growth rate calculation results.

  13. First-principles study of the band structure and optical absorption of CuGaS2

    NASA Astrophysics Data System (ADS)

    Aguilera, Irene; Vidal, Julien; Wahnón, Perla; Reining, Lucia; Botti, Silvana

    2011-08-01

    CuGaS2 is the most promising chalcopyrite host for intermediate-band thin-film solar cells. Standard Kohn-Sham density functional theory fails in describing the band structure of chalcopyrite materials, due to the strong underestimation of the band gap and the poor description of p-d hybridization, which makes it inadvisable to use this approach to study the states in the gap induced by doping. We used a state-of-the-art restricted self-consistent GW approach to determine the electronic states of CuGaS2: in the energy range of interest for optical absorption, the GW corrections shift the Kohn-Sham bands almost rigidly, as we proved through analysis of the effective masses, bandwidths, and relative position of the conduction energy valleys. Furthermore, starting from the GW quasiparticle bands, we calculated optical absorption spectra using different approximations. We show that the time-dependent density functional theory can be an efficient alternative to the solution of the Bethe-Salpeter equation when the exchange-correlation kernels derived from the Bethe-Salpeter equation are employed. This conclusion is important for further studies of optical properties of supercells including dopants.

  14. X-ray absorption and reflection as probes of the GaN conduction bands: Theory and experiments

    SciTech Connect

    Lambrecht, W.R.L.; Rashkeev, S.N.; Segall, B.

    1997-04-01

    X-ray absorption measurements are a well-known probe of the unoccupied states in a material. The same information can be obtained by using glancing angle X-ray reflectivity. In spite of several existing band structure calculations of the group III nitrides and previous optical studies in UV range, a direct probe of their conduction band densities of states is of interest. The authors performed a joint experimental and theoretical investigation using both of these experimental techniques for wurtzite GaN.

  15. 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.

  16. The Pt2 (1,0) band of System VI in the near infrared by intracavity laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    O'Brien, Leah C.; O'Brien, James J.

    2011-05-01

    Intracavity laser absorption spectroscopy has been used to record rotationally resolved electronic spectra of Pt2 in the near infrared. The metal dimers were created using a 50 mm-long, platinum-lined hollow cathode plasma discharge. The observed transition at 12 937 cm-1 is identified as the (1,0) band of System VI, with state symmetries Ω = 0 - X Ω = 0.

  17. Precise ro-vibrational analysis of molecular bands forbidden in absorption: The ν8 +ν10 band of 13C2H4

    NASA Astrophysics Data System (ADS)

    Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Kashirina, N. V.; Maul, C.; Bauerecker, S.

    2015-10-01

    The high resolution spectra of the 13C2H4 molecule was recorded with a Bruker IFS 120 Fourier transform spectrometer and theoretically analyzed in the 1650 - 1800cm-1 region of the ν8 +ν10 band which is forbidden in absorption. About 1200 experimental transitions with the maximum values of quantum numbers Jmax. = 34 and Kamax. = 17 were assigned to the ν8 +ν10 band. On that basis the 516 high accuracy ro-vibrational energies of the (v8=v10=1) vibrational state, as well as energy levels with J ≤ 2 of the (v4 =v8 = 1) and (v7 =v8 = 1) vibrational states, were determined which then were used as input data in the weighted fit of spectroscopic parameters of the Hamiltonian (strong local resonance interactions of the ν8 +ν10 band with the bands ν4 +ν8 and ν7 +ν8 have been taken into account). A set of 34 vibrational, rotational, centrifugal distortion, and resonance interaction parameters was obtained from the fit. These parameters reproduce positions of about 1200 experimentally recorded and assigned transitions with the rms error drms = 0.00018cm-1 (blended and very weak transitions are not taken into account in that case).

  18. Calibration of scalar relativistic density functional theory for the calculation of sulfur K-edge X-ray absorption spectra.

    PubMed

    Debeer George, Serena; Neese, Frank

    2010-02-15

    Sulfur K-edge X-ray absorption spectroscopy has been proven to be a powerful tool for investigating the electronic structures of sulfur-containing coordination complexes. The full information content of the spectra can be developed through a combination of experiment and time-dependent density functional theory (TD-DFT). In this work, the necessary calibration is carried out for a range of contemporary functionals (BP86, PBE, OLYP, OPBE, B3LYP, PBE0, TPSSh) in a scalar relativistic (0(th) order regular approximation, ZORA) DFT framework. It is shown that with recently developed segmented all-electron scalar relativistic (SARC) basis sets one obtains results that are as good as with large, uncontracted basis sets. The errors in the calibrated transition energies are on the order of 0.1 eV. The error in calibrated intensities is slightly larger, but the calculations are still in excellent agreement with experiment. The behavior of full TD-DFT linear response versus the Tamm-Dancoff approximation has been evaluated with the result that two methods are almost indistinguishable. The inclusion of relativistic effects barely changes the results for first row transition metal complexes, however, the contributions become visible for second-row transition metals and reach a maximum (of an approximately 10% change in the calibration parameters) for third row transition metal species. The protocol developed here is approximately 10 times more efficient than the previously employed protocol, which was based on large, uncontracted basis sets. The calibration strategy followed here may be readily extended to other edges. PMID:20092349

  19. Solvent dipole modulation of conduction band edge shift and charge recombination in robust dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Jiao, Xingjian; Li, Jianbao; Lin, Hong

    2012-12-01

    Molecular modification is certified as a powerful strategy to adjust the energy alignment and electron transfer dynamics of dye-sensitized solar cells (DSCs). Herein, devices are assembled with three robust solvent (3-methoxypropionitrile, N,N-dimethylformamide and γ-butyrolactone) based electrolytes to elucidate the solvent dipole effects at the semiconductor-dye-electrolyte interface. Photovoltaic results demonstrate that open-circuit photovoltages of the devices vary linearly with the dipole moment of the solvents, along with an adverse dependence of the short-circuit photocurrent density under simulated irradiation. Impedance analysis reveals an apparent dipole moment-modulated conduction band edge shift of the nanocrystalline TiO2 electrodes with respect to the redox potential of the electrolyte. Furthermore, the adverse shifts of the short-circuit photocurrent are explained by a dipole dependence of the driving force for electron injection and the interfacial charge recombination, together with a notably changed charge collection efficiency. Therefore, this study draws attention to the feasibility of tuning the electron transfer dynamics and energy alignment in photoelectrochemical devices by judiciously selecting the electrolyte solvents for further efficiency improvement, especially for those alternative organic sensitizers or quantum dots with inadequate electron injection driven forces.

  20. All-printable band-edge modulated ZnO nanowire photodetectors with ultra-high detectivity

    NASA Astrophysics Data System (ADS)

    Liu, Xi; Gu, Leilei; Zhang, Qianpeng; Wu, Jiyuan; Long, Yunze; Fan, Zhiyong

    2014-06-01

    High-performance photodetectors are critical for high-speed optical communication and environmental sensing, and flexible photodetectors can be used for a wide range of portable or wearable applications. Here we demonstrate the all-printable fabrication of polycrystalline nanowire-based high-performance photodetectors on flexible substrates. Systematic investigations have shown their ultra-high photoconductive gain, responsivity and detectivity up to 3.3 × 1017 Jones. Further analysis shows that their high performance originates from the unique band-edge modulation along the nanowire axial direction, where the existence of Schottky barriers in series leads to highly suppressed dark current of the device and also gives rise to fast photoelectric response to low-intensity optical signal owing to barrier height modulation. The discovered rationale in this work can be utilized as guideline to design high-performance photodetectors with other nanomaterial systems. The developed fabrication scheme opens up possibility for future flexible and high-performance integrated optoelectronic sensor circuitry.

  1. All-printable band-edge modulated ZnO nanowire photodetectors with ultra-high detectivity

    PubMed Central

    Liu, Xi; Gu, Leilei; Zhang, Qianpeng; Wu, Jiyuan; Long, Yunze; Fan, Zhiyong

    2014-01-01

    High-performance photodetectors are critical for high-speed optical communication and environmental sensing, and flexible photodetectors can be used for a wide range of portable or wearable applications. Here we demonstrate the all-printable fabrication of polycrystalline nanowire-based high-performance photodetectors on flexible substrates. Systematic investigations have shown their ultra-high photoconductive gain, responsivity and detectivity up to 3.3 × 1017 Jones. Further analysis shows that their high performance originates from the unique band-edge modulation along the nanowire axial direction, where the existence of Schottky barriers in series leads to highly suppressed dark current of the device and also gives rise to fast photoelectric response to low-intensity optical signal owing to barrier height modulation. The discovered rationale in this work can be utilized as guideline to design high-performance photodetectors with other nanomaterial systems. The developed fabrication scheme opens up possibility for future flexible and high-performance integrated optoelectronic sensor circuitry. PMID:24898081

  2. Wide angle and narrow-band asymmetric absorption in visible and near-infrared regime through lossy Bragg stacks.

    PubMed

    Shu, Shiwei; Zhan, Yawen; Lee, Chris; Lu, Jian; Li, Yang Yang

    2016-01-01

    Absorber is an important component in various optical devices. Here we report a novel type of asymmetric absorber in the visible and near-infrared spectrum which is based on lossy Bragg stacks. The lossy Bragg stacks can achieve near-perfect absorption at one side and high reflection at the other within the narrow bands (several nm) of resonance wavelengths, whereas display almost identical absorption/reflection responses for the rest of the spectrum. Meanwhile, this interesting wavelength-selective asymmetric absorption behavior persists for wide angles, does not depend on polarization, and can be ascribed to the lossy characteristics of the Bragg stacks. Moreover, interesting Fano resonance with easily tailorable peak profiles can be realized using the lossy Bragg stacks. PMID:27251768

  3. Wide angle and narrow-band asymmetric absorption in visible and near-infrared regime through lossy Bragg stacks

    NASA Astrophysics Data System (ADS)

    Shu, Shiwei; Zhan, Yawen; Lee, Chris; Lu, Jian; Li, Yang Yang

    2016-06-01

    Absorber is an important component in various optical devices. Here we report a novel type of asymmetric absorber in the visible and near-infrared spectrum which is based on lossy Bragg stacks. The lossy Bragg stacks can achieve near-perfect absorption at one side and high reflection at the other within the narrow bands (several nm) of resonance wavelengths, whereas display almost identical absorption/reflection responses for the rest of the spectrum. Meanwhile, this interesting wavelength-selective asymmetric absorption behavior persists for wide angles, does not depend on polarization, and can be ascribed to the lossy characteristics of the Bragg stacks. Moreover, interesting Fano resonance with easily tailorable peak profiles can be realized using the lossy Bragg stacks.

  4. Wide angle and narrow-band asymmetric absorption in visible and near-infrared regime through lossy Bragg stacks

    PubMed Central

    Shu, Shiwei; Zhan, Yawen; Lee, Chris; Lu, Jian; Li, Yang Yang

    2016-01-01

    Absorber is an important component in various optical devices. Here we report a novel type of asymmetric absorber in the visible and near-infrared spectrum which is based on lossy Bragg stacks. The lossy Bragg stacks can achieve near-perfect absorption at one side and high reflection at the other within the narrow bands (several nm) of resonance wavelengths, whereas display almost identical absorption/reflection responses for the rest of the spectrum. Meanwhile, this interesting wavelength-selective asymmetric absorption behavior persists for wide angles, does not depend on polarization, and can be ascribed to the lossy characteristics of the Bragg stacks. Moreover, interesting Fano resonance with easily tailorable peak profiles can be realized using the lossy Bragg stacks. PMID:27251768

  5. 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. PMID:25320052

  6. Local disorder investigation in NiS2-xSex using Raman and Ni K-edge x-ray absorption spectroscopies

    NASA Astrophysics Data System (ADS)

    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.

    2014-11-01

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS2-xSex (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 NiS2-xSex 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 NiS2-xSex pyrites.

  7. Absolute Rovibrational Intensities of C-12O2-16 Absorption Bands in the 3090-3850/ CM Spectral Region

    NASA Technical Reports Server (NTRS)

    Devi, V. Malathy; Benner, D. Chris; Rinsland, Curtis P.; Smith, Mary Ann H.

    1998-01-01

    A multispectrum nonlinear least-squares fitting technique has been used to determine the absolute intensities for approximately 1500 spectral lines in 36 vibration - rotation bands Of C-12O2-16 between 3090 and 3850/ cm. A total of six absorption spectra of a high- purity (99.995% minimum) natural sample of carbon dioxide were used in the analysis. The spectral data (0.01/cm resolution) were recorded at room temperature and low pressure (1 to 10 Torr) using the McMath-Pierce Fourier transform spectrometer of the National Solar Observatory (NSO) on Kitt Peak. The absorption path lengths for these spectra varied between 24.86 and 385.76 m. The first experimental determination of the intensity of the theoretically predicted 2(nu)(sub 2, sup 2) + nu(sub 3) "forbidden" band has been made. The measured line intensities obtained for each band have been analyzed to determine the vibrational band intensity, S(sub nu), in /cm/( molecule/sq cm) at 296 K, square of the rotationless transition dipole moment |R|(exp 2) in Debye, as well as the nonrigid rotor coefficients. The results are compared to the values listed in the 1996 HITRAN database which are obtained using the direct numerical diagonalization (DND) technique as well as to other published values where available.

  8. Analysis of airborne imaging spectrometer data for the Ruby Mountains, Montana, by use of absorption-band-depth images

    NASA Technical Reports Server (NTRS)

    Brickey, David W.; Crowley, James K.; Rowan, Lawrence C.

    1987-01-01

    Airborne Imaging Spectrometer-1 (AIS-1) data were obtained for an area of amphibolite grade metamorphic rocks that have moderate rangeland vegetation cover. Although rock exposures are sparse and patchy at this site, soils are visible through the vegetation and typically comprise 20 to 30 percent of the surface area. Channel averaged low band depth images for diagnostic soil rock absorption bands. Sets of three such images were combined to produce color composite band depth images. This relative simple approach did not require extensive calibration efforts and was effective for discerning a number of spectrally distinctive rocks and soils, including soils having high talc concentrations. The results show that the high spectral and spatial resolution of AIS-1 and future sensors hold considerable promise for mapping mineral variations in soil, even in moderately vegetated areas.

  9. Adsorption of dopamine on rutile TiO2 (110): a photoemission and near-edge X-ray absorption fine structure study.

    PubMed

    Jackman, Mark J; Syres, Karen L; Cant, David J H; Hardman, Samantha J O; Thomas, Andrew G

    2014-07-29

    Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) techniques have been used to study the adsorption of dopamine on a rutile TiO2 (110) single crystal. Photoemission results suggest that dopamine bonds through the oxygen molecules in a bidentate fashion. From the data, it is ambiguous whether the oxygens bond to the same 5-fold coordinated surface titanium atom or bridges across two, although based on the bonding of pyrocatechol on rutile TiO2 (110), it is likely that the dopamine bridges two titanium atoms. Using the searchlight effect, the carbon K-edge near-edge X-ray absorption fine structure NEXAFS spectra recorded for dopamine on rutile TiO2 (110) show the phenyl ring to be oriented at 78° ± 5° from the surface and twisted 11 ± 10° relative to the (001) direction. PMID:25003716

  10. 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. PMID:25638086

  11. Sulfur and nitrogen speciation in humic substances by x-ray absorption near-edge structure spectroscopy

    SciTech Connect

    Vairavamurthy, M.A.; Wang, Shenghe; Maletic, D.

    1996-12-31

    Understanding the chemical composition and structure of complex macromolecules in the geosphere, such as humic substances and kerogen, poses a challenging analytical problem. Widely used chromatographic techniques, such as the pyrolysis GC-MS, cause severe changes in structure during preparation and analysis of the sample, and thus, may not give accurate information. An important non-destructive technique that is becoming popular in speciation studies of environmental and geochemical samples is x-ray absorption fine structure spectroscopy. We used the x-ray absorption near-edge structure (XANFS) spectroscopy for examining the speciation of sulfur and nitrogen in humic substances of different origins, including soil and marine sediments. XANES provides information on the characteristics of the functional groups containing these atoms because of its sensitivity to the electronic structure, oxidation state, and the geometry of the neighboring atoms. Organic sulfides, di- and poly-sulfides, sulfonates and organic sulfates are the major forms of sulfur detected in all the humics we examined. The oxidized sulfonate-sulfur dominates the composition of sulfur species in soil humics accounting for more than 60% of the total sulfur. In marine humics, although sulfonates are abundant in near-surface sediments, reduced sulfur species, particularly di-and poly-sulfides, also constitute an important fraction. The nitrogen XANES indicates the dominance of amino and amide groups among nitrogen functionalities, although porphyrinic and pyridinic groups also are present. The significance of these results for the transformations of nitrogen and sulfur in soil and sedimentary systems will be presented.

  12. Molybdenum X-ray absorption edges from 200 to 20,000eV: the benefits of soft X-ray spectroscopy for chemical speciation.

    PubMed

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

    2009-02-01

    We have surveyed the chemical utility of the near-edge structure of molybdenum X-ray absorption edges from the hard X-ray K-edge at 20,000eV down to the soft X-ray M(4,5)-edges at approximately 230eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO(4)(2-) and MoS(4)(2-). We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO(4)(2-) and MoS(4)(2-) and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L(2,3)-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft X-ray M(2,3)-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L(2,3)-edges. Interestingly, the soft X-ray, low energy ( approximately 230eV) M(4,5)-edges had greatest potential chemical sensitivity and using our high-resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d-->5p transitions, while the broad edge structure has predominately 3d-->4f character. A proper understanding of the dependence of these soft X-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M(4,5)-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

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

    PubMed Central

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

    2009-01-01

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

  14. Voigt deconvolution method and its applications to pure oxygen absorption spectrum at 1270 nm band

    NASA Astrophysics Data System (ADS)

    AL-Jalali, Muhammad A.; Aljghami, Issam F.; Mahzia, Yahia M.

    2016-03-01

    Experimental spectral lines of pure oxygen at 1270 nm band were analyzed by Voigt deconvolution method. The method gave a total Voigt profile, which arises from two overlapping bands. Deconvolution of total Voigt profile leads to two Voigt profiles, the first as a result of O2 dimol at 1264 nm band envelope, and the second from O2 monomer at 1268 nm band envelope. In addition, Voigt profile itself is the convolution of Lorentzian and Gaussian distributions. Competition between thermal and collisional effects was clearly observed through competition between Gaussian and Lorentzian width for each band envelope. Voigt full width at half-maximum height (Voigt FWHM) for each line, and the width ratio between Lorentzian and Gaussian width (ΓLΓG- 1) have been investigated. The following applied pressures were at 1, 2, 3, 4, 5, and 8 bar, while the temperatures were at 298 K, 323 K, 348 K, and 373 K range.

  15. Voigt deconvolution method and its applications to pure oxygen absorption spectrum at 1270 nm band.

    PubMed

    Al-Jalali, Muhammad A; Aljghami, Issam F; Mahzia, Yahia M

    2016-03-15

    Experimental spectral lines of pure oxygen at 1270 nm band were analyzed by Voigt deconvolution method. The method gave a total Voigt profile, which arises from two overlapping bands. Deconvolution of total Voigt profile leads to two Voigt profiles, the first as a result of O2 dimol at 1264 nm band envelope, and the second from O2 monomer at 1268 nm band envelope. In addition, Voigt profile itself is the convolution of Lorentzian and Gaussian distributions. Competition between thermal and collisional effects was clearly observed through competition between Gaussian and Lorentzian width for each band envelope. Voigt full width at half-maximum height (Voigt FWHM) for each line, and the width ratio between Lorentzian and Gaussian width (ΓLΓG(-1)) have been investigated. The following applied pressures were at 1, 2, 3, 4, 5, and 8 bar, while the temperatures were at 298 K, 323 K, 348 K, and 373 K range. PMID:26709019

  16. 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. PMID:26502979

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

    SciTech Connect

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

    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{sup 5}) model systems with well-known electronic structure, viz., atomic Fe{sup 3+}, high-spin [FeCl{sub 6}]{sup 3−} with ligand donor bonding, and low-spin [Fe(CN){sub 6}]{sup 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.

  18. Derivation of absorption coefficient and reduced scattering coefficient with edge-loss method and comparison with video reflectometry method

    NASA Astrophysics Data System (ADS)

    Yoshida, Kenichiro

    2016-08-01

    We derived the absorption coefficient ( μ a) and the reduced scattering coefficient ( μ s') using the edge-loss method (ELM) and the video reflectometry method (VRM), and compared the results. In a previous study, we developed the ELM to easily evaluate the lateral spread in the skin; the VRM is a conventional method. The ELM measures the translucency index, which is correlated with μ a and μ s'. To obtain a precise estimation of these parameters, we improved the treatment of a white standard and the surface reflection. For both skin phantoms and actual skin, the values for μ a and μ s' that we obtained using the ELM were similar to those obtained using the VRM, when μ a/ μ s' was less than or equal to 0.05 and the diffusion approximation was applicable. Under this condition, the spectral reflectivity is greater than 0.4. In this study, we considered wavelengths longer than 600 nm for Types III and IV of the Fitzpatrick scale. For skin, the repeatability errors of the parameters obtained with the ELM were smaller than those obtained with the VRM; this can be an advantage in field tests.

  19. Speciation of sulfur in humic and fulvic acids using X-ray Absorption Near-Edge Structures (XANES) spectroscopy

    SciTech Connect

    Morra, M.J.; Fendorf, S.E.; Brown, P.D.

    1997-02-01

    Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils. 27 refs., 4 figs., 3 tabs.

  20. Determining Orientational Structure of Diamondoid Thiols Attached to Silver Using Near Edge X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Willey, T M; Lee, J I; Fabbri, J D; Wang, D; Nielsen, M; Randel, J C; Schreiner, P R; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J P; Carlson, R K; Terminello, L J; Melosh, N A; van Buuren, T

    2008-10-07

    Near-edge x-ray absorption fine structure spectroscopy (NEXAFS) is a powerful tool for determination of molecular orientation in self-assembled monolayers and other surface-attached molecules. A general framework for using NEXAFS to simultaneously determine molecular tilt and twist of rigid molecules attached to surfaces is presented. This framework is applied to self-assembled monolayers of higher diamondoid, hydrocarbon molecules with cubic-diamond-cage structures. Diamondoid monolayers chemisorbed on metal substrates are known to exhibit interesting electronic and surface properties. This work compares molecular orientation in monolayers prepared on silver substrates using two different thiol positional isomers of [121]tetramantane, and thiols derived from two different pentamantane structural isomers, [1212]pentamantane and [1(2,3)4]pentamantane. The observed differences in monolayer structure demonstrate the utility and limitations of NEXAFS spectroscopy and the framework. The results also demonstrate the ability to control diamondoid assembly, in particular the molecular orientational structure, providing a flexible platform for the modification of surface properties with this exciting new class of nanodiamond materials.

  1. Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy

    NASA Astrophysics Data System (ADS)

    Morra, Matthew J.; Fendorf, Scott E.; Brown, Paul D.

    1997-02-01

    Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils.

  2. Derivation of absorption coefficient and reduced scattering coefficient with edge-loss method and comparison with video reflectometry method

    NASA Astrophysics Data System (ADS)

    Yoshida, Kenichiro

    2016-07-01

    We derived the absorption coefficient (μ a) and the reduced scattering coefficient (μ s') using the edge-loss method (ELM) and the video reflectometry method (VRM), and compared the results. In a previous study, we developed the ELM to easily evaluate the lateral spread in the skin; the VRM is a conventional method. The ELM measures the translucency index, which is correlated with μ a and μ s'. To obtain a precise estimation of these parameters, we improved the treatment of a white standard and the surface reflection. For both skin phantoms and actual skin, the values for μ a and μ s' that we obtained using the ELM were similar to those obtained using the VRM, when μ a/μ s' was less than or equal to 0.05 and the diffusion approximation was applicable. Under this condition, the spectral reflectivity is greater than 0.4. In this study, we considered wavelengths longer than 600 nm for Types III and IV of the Fitzpatrick scale. For skin, the repeatability errors of the parameters obtained with the ELM were smaller than those obtained with the VRM; this can be an advantage in field tests.

  3. Time-Resolved IR-Absorption Spectroscopy of Hot-Electron Dynamics in Satellite and Upper Conduction Bands in GaP

    NASA Technical Reports Server (NTRS)

    Cavicchia, M. A.; Alfano, R. R.

    1995-01-01

    The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.

  4. 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). PMID:17429991

  5. Screened coulomb hybrid DFT investigation of band gap and optical absorption predictions of CuVO3, CuNbO3 and Cu5Ta11O30 materials.

    PubMed

    Harb, Moussab; Masih, Dilshad; Takanabe, Kazuhiro

    2014-09-14

    We present a joint theoretical and experimental investigation of the optoelectronic properties of CuVO3, CuNbO3 and Cu5Ta11O30 materials for potential photocatalytic and solar cell applications. In addition to the experimental results obtained by powder X-ray diffraction and UV-Vis spectroscopy of the materials synthesized under flowing N2 gas at atmospheric pressure via solid-state reactions, the electronic structure and the UV-Vis optical absorption coefficient of these compounds are predicted with high accuracy using advanced first-principles quantum methods based on DFT (including the perturbation theory approach DFPT) within the screened coulomb hybrid HSE06 exchange-correlation formalism. The calculated density of states are found to be in agreement with the UV-Vis diffuse reflectance spectra, predicting a small indirect band gap of 1.4 eV for CuVO3, a direct band gap of 2.6 eV for CuNbO3, and an indirect (direct) band gap of 2.1 (2.6) eV for Cu5Ta11O30. It is confirmed that the Cu(I)-based multi-metal oxides possess a strong contribution of filled Cu(I) states in the valence band and of empty d(0) metal states in the conduction band. Interestingly, CuVO3 with its predicted small indirect band gap of 1.4 eV shows the highest absorption coefficient in the visible range with a broad absorption edge extending to 886 nm. This novel result offers a great opportunity for this material to be an excellent candidate for solar cell applications. PMID:25055167

  6. Ground-based Photon Path Measurements from Solar Absorption Spectra of the O2 A-band

    NASA Technical Reports Server (NTRS)

    Yang, Z.; Wennberg, P. O.; Cageao, R. P.; Pongetti, T. J.; Toon, G. C.; Sander, S. P.

    2005-01-01

    High-resolution solar absorption spectra obtained from Table Mountain Facility (TMF, 34.38degN, 117.68degW, 2286 m elevation) have been analyzed in the region of the O2 A-band. The photon paths of direct sunlight in clear sky cases are retrieved from the O2 absorption lines and compared with ray-tracing calculations based on the solar zenith angle and surface pressure. At a given zenith angle, the ratios of retrieved to geometrically derived photon paths are highly precise (approx.0.2%), but they vary as the zenith angle changes. This is because current models of the spectral lineshape in this band do not properly account for the significant absorption that exists far from the centers of saturated lines. For example, use of a Voigt function with Lorentzian far wings results in an error in the retrieved photon path of as much as 5%, highly correlated with solar zenith angle. Adopting a super-Lorentz function reduces, but does not completely eliminate this problem. New lab measurements of the lineshape are required to make further progress.

  7. L-edge x-ray absorption fine structure study of growth and morphology of ultrathin nickel films deposited on copper

    SciTech Connect

    Nietubyc, Robert; Foehlisch, Alexander; Glaser, Leif; Lau, Julian Tobias; Martins, Michael; Reif, Matthias; Wurth, Wilfried

    2004-12-15

    We have studied the Ni L edge x-ray absorption fine structure for thin Ni films evaporated on a Cu(001) substrate. The measurements have been carried out for films having coverages ranging from 0.07 monolayers (ML) up to 3.1 ML. The coverage has been calibrated using the ratio of the Ni L{sub 3} to Cu L{sub 3} edge jump heights and independently verified with titration experiments. We have found a clear evolution of the x-ray absorption fine structure at the Ni L{sub 3} edge with coverage. To interpret the measured spectra first-principles calculations have been performed modeling a two-dimensional growth. The calculations reproduced all features observed experimentally. From the comparison between experiment and theory we can conclude that submonolayer films contain a large number of small islands. Deposition of an amount of nickel corresponding to a single layer results in the formation of an almost perfect flat layer. Our studies show that L edge x-ray absorption spectroscopy can provide useful information on thin-film growth and morphology.

  8. Semi-Empirical Validation of the Cross-Band Relative Absorption Technique for the Measurement of Molecular Mixing Ratios

    NASA Technical Reports Server (NTRS)

    Pliutau, Denis; Prasad, Narasimha S

    2013-01-01

    Studies were performed to carry out semi-empirical validation of a new measurement approach we propose for molecular mixing ratios determination. The approach is based on relative measurements in bands of O2 and other molecules and as such may be best described as cross band relative absorption (CoBRA). . The current validation studies rely upon well verified and established theoretical and experimental databases, satellite data assimilations and modeling codes such as HITRAN, line-by-line radiative transfer model (LBLRTM), and the modern-era retrospective analysis for research and applications (MERRA). The approach holds promise for atmospheric mixing ratio measurements of CO2 and a variety of other molecules currently under investigation for several future satellite lidar missions. One of the advantages of the method is a significant reduction of the temperature sensitivity uncertainties which is illustrated with application to the ASCENDS mission for the measurement of CO2 mixing ratios (XCO2). Additional advantages of the method include the possibility to closely match cross-band weighting function combinations which is harder to achieve using conventional differential absorption techniques and the potential for additional corrections for water vapor and other interferences without using the data from numerical weather prediction (NWP) models.

  9. Semi-empirical validation of the cross-band relative absorption technique for the measurement of molecular mixing ratios

    NASA Astrophysics Data System (ADS)

    Pliutau, Denis; Prasad, Narasimha S.

    2013-05-01

    Studies were performed to carry out semi-empirical validation of a new measurement approach we propose for molecular mixing ratios determination. The approach is based on relative measurements in bands of O2 and other molecules and as such may be best described as cross band relative absorption (CoBRA). The current validation studies rely upon well verified and established theoretical and experimental databases, satellite data assimilations and modeling codes such as HITRAN, line-by-line radiative transfer model (LBLRTM), and the modern-era retrospective analysis for research and applications (MERRA). The approach holds promise for atmospheric mixing ratio measurements of CO2 and a variety of other molecules currently under investigation for several future satellite lidar missions. One of the advantages of the method is a significant reduction of the temperature sensitivity uncertainties which is illustrated with application to the ASCENDS mission for the measurement of CO2 mixing ratios (XCO2). Additional advantages of the method include the possibility to closely match cross-band weighting function combinations which is harder to achieve using conventional differential absorption techniques and the potential for additional corrections for water vapor and other interferences without using the data from numerical weather prediction (NWP) models.

  10. Bandgap and optical absorption edge of GaAs1-xBix alloys with 0 < x < 17.8%

    NASA Astrophysics Data System (ADS)

    Masnadi-Shirazi, M.; Lewis, R. B.; Bahrami-Yekta, V.; Tiedje, T.; Chicoine, M.; Servati, P.

    2014-12-01

    The compositional dependence of the fundamental bandgap of pseudomorphic GaAs1-xBix layers on GaAs substrates is studied at room temperature by optical transmission and photoluminescence spectroscopies. All GaAs1-xBix films (0 ≤ x ≤ 17.8%) show direct optical bandgaps, which decrease with increasing Bi content, closely following density functional theory predictions. The smallest measured bandgap is 0.52 eV (˜2.4 μm) at 17.8% Bi. Extrapolating a fit to the data, the GaAs1-xBix bandgap is predicted to reach 0 eV at 35% Bi. Below the GaAs1-xBix bandgap, exponential absorption band tails are observed with Urbach energies 3-6 times larger than that of bulk GaAs. The Urbach parameter increases with Bi content up to 5.5% Bi, and remains constant at higher concentrations. The lattice constant and Bi content of GaAs1-xBix layers (0 < x ≤ 19.4%) are studied using high resolution x-ray diffraction and Rutherford backscattering spectroscopy. The relaxed lattice constant of hypothetical zincblende GaBi is estimated to be 6.33 ± 0.05 Å, from extrapolation of the Rutherford backscattering spectrometry and x-ray diffraction data.

  11. Measurement of InAsSb bandgap energy and InAs/InAsSb band edge positions using spectroscopic ellipsometry and photoluminescence spectroscopy

    SciTech Connect

    Webster, P. T.; Riordan, N. A.; Liu, S.; Zhang, Y.-H.; Johnson, S. R.; Steenbergen, E. H.

    2015-12-28

    The structural and optical properties of lattice-matched InAs{sub 0.911}Sb{sub 0.089} bulk layers and strain-balanced InAs/InAs{sub 1−x}Sb{sub x} (x ∼ 0.1–0.4) superlattices grown on (100)-oriented GaSb substrates by molecular beam epitaxy are examined using X-ray diffraction, spectroscopic ellipsometry, and temperature dependent photoluminescence spectroscopy. The photoluminescence and ellipsometry measurements determine the ground state bandgap energy and the X-ray diffraction measurements determine the layer thickness and mole fraction of the structures studied. Detailed modeling of the X-ray diffraction data is employed to quantify unintentional incorporation of approximately 1% Sb into the InAs layers of the superlattices. A Kronig-Penney model of the superlattice miniband structure is used to analyze the valence band offset between InAs and InAsSb, and hence the InAsSb band edge positions at each mole fraction. The resulting composition dependence of the bandgap energy and band edge positions of InAsSb are described using the bandgap bowing model; the respective low and room temperature bowing parameters for bulk InAsSb are 938 and 750 meV for the bandgap, 558 and 383 meV for the conduction band, and −380 and −367 meV for the valence band.

  12. Measurement of InAsSb bandgap energy and InAs/InAsSb band edge positions using spectroscopic ellipsometry and photoluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Webster, P. T.; Riordan, N. A.; Liu, S.; Steenbergen, E. H.; Synowicki, R. A.; Zhang, Y.-H.; Johnson, S. R.

    2015-12-01

    The structural and optical properties of lattice-matched InAs0.911Sb0.089 bulk layers and strain-balanced InAs/InAs1-xSbx (x ˜ 0.1-0.4) superlattices grown on (100)-oriented GaSb substrates by molecular beam epitaxy are examined using X-ray diffraction, spectroscopic ellipsometry, and temperature dependent photoluminescence spectroscopy. The photoluminescence and ellipsometry measurements determine the ground state bandgap energy and the X-ray diffraction measurements determine the layer thickness and mole fraction of the structures studied. Detailed modeling of the X-ray diffraction data is employed to quantify unintentional incorporation of approximately 1% Sb into the InAs layers of the superlattices. A Kronig-Penney model of the superlattice miniband structure is used to analyze the valence band offset between InAs and InAsSb, and hence the InAsSb band edge positions at each mole fraction. The resulting composition dependence of the bandgap energy and band edge positions of InAsSb are described using the bandgap bowing model; the respective low and room temperature bowing parameters for bulk InAsSb are 938 and 750 meV for the bandgap, 558 and 383 meV for the conduction band, and -380 and -367 meV for the valence band.

  13. Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

    SciTech Connect

    Picconi, David; Grebenshchikov, Sergy Yu.

    2014-08-21

    Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadening of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.

  14. Quantitative Evaluation of the Carbon Hybridization State by Near Edge X-ray Absorption Fine Structure Spectroscopy.

    PubMed

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

    2016-03-01

    The characterization of the local bonding configuration of carbon in carbon-based materials is of paramount importance since the properties of such materials strongly depend on the distribution of carbon hybridization states, the local ordering, and the degree of hydrogenation. Carbon 1s near edge X-ray absorption fine structure (NEXAFS) spectroscopy is one of the most powerful techniques for gaining insights into the bonding configuration of near-surface carbon atoms. The common methodology for quantitatively evaluating the carbon hybridization state using C 1s NEXAFS measurements, which is based on the analysis of the sample of interest and of a highly ordered pyrolytic graphite (HOPG) reference sample, was reviewed and critically assessed, noting that inconsistencies are found in the literature in applying this method. A theoretical rationale for the specific experimental conditions to be used for the acquisition of HOPG reference spectra is presented together with the potential sources of uncertainty and errors in the correctly computed fraction of sp(2)-bonded carbon. This provides a specific method for analyzing the distribution of carbon hybridization state using NEXAFS spectroscopy. As an illustrative example, a hydrogenated amorphous carbon film was analyzed using this method and showed good agreement with X-ray photoelectron spectroscopy (which is surface sensitive). Furthermore, the results were consistent with analysis from Raman spectroscopy (which is not surface sensitive), indicating the absence of a structurally different near-surface region in this particular thin film material. The present work can assist surface scientists in the analysis of NEXAFS spectra for the accurate characterization of the structure of carbon-based materials. PMID:26814796

  15. H2 Photogeneration Using a Phosphonate-Anchored Ni-PNP Catalyst on a Band-Edge-Modified p-Si(111)|AZO Construct.

    PubMed

    Kim, Hark Jin; Seo, Junhyeok; Rose, Michael J

    2016-01-20

    We report the fabrication of a {semiconductor}|{metal oxide}|{molecular catalyst} construct for the photogeneration of dihydrogen (H2) under illumination, including band-edge modulation of the semiconductor electrode depending on the identity of Si(111)-R and the metal oxide. Briefly, a synergistic band-edge modulation is observed upon (i) the introduction of a p-Si|n-AZO heterojunction and (ii) introduction of an organic dimethoxyphenyl (diMeOPh) group at the heterojunction interface; the AZO also serves as a transparent and conductive conduit, which was capped with an ultrathin layer (20 Å) of amorphous TiO2 for stability. A phosphonate-appended PNP ligand and its Ni complex were then adsorbed to the p/n heterojunction for photoelectrochemical H2 generation (figures of merit: Vonset ≈ + 0.03 V vs NHE, Jmax ≈ 8 mA cm(-2) at 60 mM TsOH). PMID:26741653

  16. Higher-order mode absorption measurement of X-band choke-mode cavities in a radial line structure

    NASA Astrophysics Data System (ADS)

    Zha, Hao; Shi, Jiaru; Wu, Xiaowei; Chen, Huaibi

    2016-04-01

    An experiment is presented to study the higher-order mode (HOM) suppression of X-band choke-mode structures with a vector network analyzer (VNA). Specific radial line disks were built to test the reflection from the corresponding damping load and different choke geometries. The mismatch between the radial lines and the VNA was calibrated through a special multi-short-load calibration method. The measured reflections of different choke geometries showed good agreement with the theoretical calculations and verified the HOM absorption feature of each geometric design.

  17. Analysis of functional groups in atmospheric aerosols by infrared spectroscopy: sparse methods for statistical selection of relevant absorption bands

    NASA Astrophysics Data System (ADS)

    Takahama, Satoshi; Ruggeri, Giulia; Dillner, Ann M.

    2016-07-01

    Various vibrational modes present in molecular mixtures of laboratory and atmospheric aerosols give rise to complex Fourier transform infrared (FT-IR) absorption spectra. Such spectra can be chemically informative, but they often require sophisticated algorithms for quantitative characterization of aerosol composition. Naïve statistical calibration models developed for quantification employ the full suite of wavenumbers available from a set of spectra, leading to loss of mechanistic interpretation between chemical composition and the resulting changes in absorption patterns that underpin their predictive capability. Using sparse representations of the same set of spectra, alternative calibration models can be built in which only a select group of absorption bands are used to make quantitative prediction of various aerosol properties. Such models are desirable as they allow us to relate predicted properties to their underlying molecular structure. In this work, we present an evaluation of four algorithms for achieving sparsity in FT-IR spectroscopy calibration models. Sparse calibration models exclude unnecessary wavenumbers from infrared spectra during the model building process, permitting identification and evaluation of the most relevant vibrational modes of molecules in complex aerosol mixtures required to make quantitative predictions of various measures of aerosol composition. We study two types of models: one which predicts alcohol COH, carboxylic COH, alkane CH, and carbonyl CO functional group (FG) abundances in ambient samples based on laboratory calibration standards and another which predicts thermal optical reflectance (TOR) organic carbon (OC) and elemental carbon (EC) mass in new ambient samples by direct calibration of infrared spectra to a set of ambient samples reserved for calibration. We describe the development and selection of each calibration model and evaluate the effect of sparsity on prediction performance. Finally, we ascribe

  18. Band Structure of the Rhodobacter sphaeroides Photosynthetic Reaction Center from Low-Temperature Absorption and Hole-Burned Spectra.

    PubMed

    Rancova, Olga; Jankowiak, Ryszard; Kell, Adam; Jassas, Mahboobe; Abramavicius, Darius

    2016-06-30

    Persistent/transient spectral hole burning (HB) and computer simulations are used to provide new insight into the excitonic structure and excitation energy transfer of the widely studied bacterial reaction center (bRC) of Rhodobacter (Rb.) sphaeroides. We focus on site energies of its cofactors and electrochromic shifts induced in the chemically oxidized (P(+)) and charge-separated (P(+)QM(-)) states. Theoretical models lead to two alternative interpretations of the H-band. On the basis of our experimental and simulation data, we suggest that the bleach near 813-825 nm in transient HB spectra in the P(+)QM(-) state, often assigned to the upper exciton component of the special pair, is mostly due to different electrochromic shifts of the BL/M cofactors. From the exciton compositions in the charge-neutral (CN) bRC, the weak fourth excitonic band near 780 nm can be denoted PY+, that is, the upper excitonic band of the special pair, which in the CN bRC behaves as a delocalized state over PM and PL pigments that weakly mixes with accessory BChls. Thus, the shoulder in the absorption of Rb. sphaeroides near 813-815 nm does not contain the PY+ exciton band. PMID:27266271

  19. Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy.

    PubMed

    Chiang, Kai-Ying; Chen, Tsan-Yao; Lee, Chih-Hao; Lin, Tsang-Lang; Wang, Ming-Kuang; Jang, Ling-Yun; Lee, Jyh-Fu

    2013-03-01

    This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan, using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry. Total arsenic (As) concentrations in the soil were more than 200 mg/kg. Over four months of laboratory experiments, less than 0.8% As was released into solution after reduction experiments. The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase. The kinetic dissolution and re-precipitation of As, Fe, Pb and sulfate in this area of paddy soils merits further study. PMID:23923437

  20. A microsecond time resolved x-ray absorption near edge structure synchrotron study of phase transitions in Fe undergoing ramp heating at high pressure

    SciTech Connect

    Marini, C.; Mathon, O.; Pascarelli, S.; Occelli, F.; Torchio, R.; Recoules, V.; Loubeyre, P.

    2014-03-07

    We report a microsecond time-resolved x-ray absorption near edge structure study using synchrotron radiation to dynamically detect structural phase transitions in Fe undergoing rapid heating along a quasi-isochoric path. Within a few ms, we observed two structural phase transitions, which transform the ambient bcc phase of Fe into the fcc phase, and then into the liquid phase. This example illustrates the opportunities offered by energy dispersive x-ray absorption spectroscopy in the study of matter under extreme dynamic conditions. Advanced simulations are compared to these data.

  1. X-ray absorption resonances near L2,3-edges from real-time propagation of the Dirac-Kohn-Sham density matrix.

    PubMed

    Kadek, Marius; Konecny, Lukas; Gao, Bin; Repisky, Michal; Ruud, Kenneth

    2015-09-21

    The solution of the Liouville-von Neumann equation in the relativistic Dirac-Kohn-Sham density matrix formalism is presented and used to calculate X-ray absorption cross sections. Both dynamical relaxation effects and spin-orbit corrections are included, as demonstrated by calculations of the X-ray absorption of SF6 near the sulfur L2,3-edges. We also propose an analysis facilitating the interpretation of spectral transitions from real-time simulations, and a selective perturbation that eliminates nonphysical excitations that are artifacts of the finite basis representation. PMID:26268195

  2. Evidence of a Shockley-Read-Hall Defect State Independent of Band-Edge Energy in InAs/In(As,Sb) Type-II Superlattices

    DOE PAGESBeta

    Aytac, Y.; Olson, B. V.; Kim, J. K.; Shaner, E. A.; Hawkins, S. D.; Klem, J. F.; Flatté, M. E.; Boggess, T. F.

    2016-05-24

    A set of seven InAs/InAsSb type-II superlattices (T2SLs) were designed to have speci c bandgap energies between 290 meV (4.3 m) and 135 meV (9.2 m) in order to study the e ects of the T2SL bandgap energy on the minority carrier lifetime. A temperature dependent optical pump-probe technique is used to measure the carrier lifetimes, and the e ect of a mid-gap defect level on the carrier recombination dynamics is reported. The Shockley-Read-Hall (SRH) defect state is found to be at energy of approximately -250 12 meV relative to the valence band edge of bulk GaSb for the entiremore » set of T2SL structures, even though the T2SL valence band edge shifts by 155 meV on the same scale. These results indicate that the SRH defect state in InAs/InAsSb T2SLs is singular and is nearly independent of the exact position of the T2SL bandgap or band edge energies. They also suggest the possibility of engineering the T2SL structure such that the SRH state is removed completely from the bandgap, a result that should signi cantly increase the minority carrier lifetime.« less

  3. Iron absorption band analysis for the discrimination of iron rich zones

    NASA Technical Reports Server (NTRS)

    Rowan, L. C. (Principal Investigator)

    1973-01-01

    The author has identified the following significant results. A lineament study of the Nevada test site is near completion. Two base maps (1:500,000) have been prepared, one of band 7 lineaments and the other of band 5 lineaments. In general, more lineaments and more faults are seen on band 5. About 45% of the lineaments appear to be faults and contacts, the others being predominantly streams, roads, railway tracks, and mountain crests. About 25% of the lineaments are unidentified so far. Special attention is being given to unmapped extensions of faults, groups of unmapped lineaments, and known mineralized areas and alteration zones. Earthquake epicenters recorded from 1869 to 1963 have been plotted on the two base maps. Preliminary examination as yet indicates no basic correlation with the lineaments. Attempts are being made to subtract bands optically, using an I2S viewer, an enlarger, and a data color viewer. Success has been limited so far due to technical difficulties, mainly vignetting and poor light sources, within the machines. Some vegetation and rock type differences, however, have been discerned.

  4. Origin of improved scintillation efficiency in (Lu,Gd){sub 3}(Ga,Al){sub 5}O{sub 12}:Ce multicomponent garnets: An X-ray absorption near edge spectroscopy study

    SciTech Connect

    Wu, Yuntao Luo, Jialiang; Ren, Guohao; Nikl, Martin

    2014-01-01

    In the recent successful improvement of scintillation efficiency in Lu{sub 3}Al{sub 5}O{sub 12}:Ce driven by Ga{sup 3+} and Gd{sup 3+} admixture, the “band-gap engineering” and energy level positioning have been considered the valid strategies so far. This study revealed that this improvement was also associated with the cerium valence instability along with the changes of chemical composition. By utilizing X-ray absorption near edge spectroscopy technique, tuning the Ce{sup 3+}/Ce{sup 4+} ratio by Ga{sup 3+} admixture was evidenced, while it was kept nearly stable with the Gd{sup 3+} admixture. Ce valence instability and Ce{sup 3+}/Ce{sup 4+} ratio in multicomponent garnets can be driven by the energy separation between 4f ground state of Ce{sup 3+} and Fermi level.

  5. Inhomogeneous broadening and peak shift of the 7.6 eV optical absorption band of oxygen vacancies in SiO{sub 2}

    SciTech Connect

    Kajihara, Koichi; Skuja, Linards; Hosono, Hideo

    2014-10-21

    The peak parameters of radiation-induced 7.6 eV optical absorption band of oxygen vacancies (Si-Si bonds) were examined for high-purity synthetic α-quartz and amorphous SiO{sub 2} (a‐SiO{sub 2}) exposed to {sup 60}Co γ-rays. The peak shape is asymmetric with the steeper edge at the lower energy side both in α-quartz and a‐SiO{sub 2}, and the peak energy is larger for α-quartz than that for a‐SiO{sub 2}. The full width at half maximum for a‐SiO{sub 2} is larger by ∼40-60% than that for α-quartz, and it increases with an increase in the disorder of the a‐SiO{sub 2} network, which is enhanced by raising the temperature of preannealing before irradiation, i.e., fictive temperature. These data are interpreted from the viewpoint of the site-to-site distribution of the Si-Si bond length in a‐SiO{sub 2}.

  6. X-ray absorption spectroscopy by full-field X-ray microscopy of a thin graphite flake: Imaging and electronic structure via the carbon K-edge

    PubMed Central

    Hitchock, Adam P; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris P; Guttmann, Peter

    2012-01-01

    Summary We demonstrate that near-edge X-ray-absorption fine-structure spectra combined with full-field transmission X-ray microscopy can be used to study the electronic structure of graphite flakes consisting of a few graphene layers. The flake was produced by exfoliation using sodium cholate and then isolated by means of density-gradient ultracentrifugation. An image sequence around the carbon K-edge, analyzed by using reference spectra for the in-plane and out-of-plane regions of the sample, is used to map and spectrally characterize the flat and folded regions of the flake. Additional spectral features in both π and σ regions are observed, which may be related to the presence of topological defects. Doping by metal impurities that were present in the original exfoliated graphite is indicated by the presence of a pre-edge signal at 284.2 eV. PMID:23016137

  7. Absolute determination of charge-coupled device quantum detection efficiency using Si K-edge x-ray absorption fine structure

    SciTech Connect

    Dunn, J; Steel, A B

    2012-05-06

    We report a method to determine the quantum detection efficiency and the absorbing layers on a front-illuminated charge-coupled device (CCD). The CCD under study, as part of a crystal spectrometer, measures intense continuum x-ray emission from a picosecond laser-produced plasma and spectrally resolves the Si K-edge x-ray absorption fine structure features due to the electrode gate structure of the device. The CCD response across the Si K-edge shows a large discontinuity as well as a number of oscillations that are identified individually and uniquely from Si, SiO{sub 2}, and Si{sub 3}N{sub 4} layers. From the spectral analysis of the structure and K-edge discontinuity, the active layer thickness and the different absorbing layers thickness can be determined precisely. A precise CCD detection model from 0.2-10 keV can be deduced from this highly sensitive technique.

  8. Simulating Cl K-edge X-ray absorption spectroscopy in MCl62- (M= U, Np, Pu) complexes and UOCl5- using time-dependent density functional theory

    SciTech Connect

    Govind, Niranjan; De Jong, Wibe A.

    2014-02-21

    We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.

  9. Simulating Ru L3-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, N.; Schoenlein, R. W.; Govind, Niranjan; Khalil, Munira

    2013-05-01

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

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

    SciTech Connect

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

    2013-04-26

    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.

  11. High resolution absorption spectroscopy of the ν1=2-6 acetylenic overtone bands of propyne: Spectroscopy and dynamics

    NASA Astrophysics Data System (ADS)

    Campargue, A.; Biennier, L.; Garnache, A.; Kachanov, A.; Romanini, D.; Herman, M.

    1999-11-01

    The rotationally resolved nν1 (n=2-6) overtone transitions of the CH acetylenic stretching of propyne (CH3-C≡C-H) have been recorded by using Fourier transform spectroscopy (n=2), various intracavity laser absorption spectrometers (n=3, 4, and 6) and cavity ring down spectroscopy (CRDS) (n=5). The 2ν1, 3ν1, and 6ν1 bands exhibit a well-resolved and mostly unperturbed J-rotational structure, whose analysis is reported. The 5ν1 band recorded by pulsed CRDS shows an unresolved rotational envelope. In the region of 12 700 cm-1, an anharmonic interaction is confirmed between 4ν1 and 3ν1+ν3+ν5. The band at a higher wave number in this dyad exhibits a partly resolved K-structure, whose analysis is reported. The mixing coefficient of the two interacting states is determined consistently using different procedures. The 1/35 anharmonic resonance evidenced in the 4ν1 manifold induces weaker intensity borrowing from the 2ν1 and 3ν1 levels to the ν1+ν3+ν5 and 2ν1+ν3+ν5 level, respectively, which have been predicted and identified. Several hot bands around the 2ν1, 3ν1, and 3ν1+ν3+ν5 bands arising from the ν9=1 and ν10=1 and 2 bending levels are identified and rotationally analyzed, also leading to determine x1,9 [-20.3(3) cm-1], x1,10 [-1.7975(75) cm-1], and x3,10 [-6.56 cm-1]. The J-clumps of the P and R branches in the 6ν1 band at 18 499 cm-1 show a Lorentzian homogeneous profile mostly J-independent with an average full width at half maximum (FWHM) of 0.17 cm-1, attributed to arising from the intramolecular vibrational energy redistribution towards the bath of vibrational states. A detailed comparative examination of the fine structure in all investigated nν1 (n=2 to 7) overtone bands and the similar behavior of the cold and hot bands arising from ν10=1 definitively suggests that a highly specific low-order anharmonic coupling, still unidentified, dominates the hierarchy of interaction mechanisms connecting the nν1 levels to the background

  12. Development of a narrow-band, tunable, frequency-quadrupled diode laser for UV absorption spectroscopy.

    PubMed

    Koplow, J P; Kliner, D A; Goldberg, L

    1998-06-20

    A compact, lightweight, low-power-consumption source of tunable, narrow-bandwidth blue and UV radiation is described. In this source, a single-longitudinal-mode diode laser seeds a pulsed, GaAlAs tapered amplifier whose ~860-nm output is frequency quadrupled by two stages of single-pass frequency doubling. Performance of the laser system is characterized over a wide range of amplifier duty cycles (0.1-1.0), pulse durations (50 ns-1.0 mus), peak currents (absorption spectra of nitric oxide and sulfur dioxide near 215 nm; the SO(2) spectrum was found to have significantly more structure and higher peak absorption cross sections than previously reported. PMID:18273363

  13. Narrow-band, tunable, semiconductor-laser-based source for deep-UV absorption spectroscopy.

    PubMed

    Kliner, D A; Koplow, J P; Goldberg, L

    1997-09-15

    Tunable, narrow-bandwidth (<200-MHz), ~215-nm radiation was produced by frequency quadrupling the ~860-nm output of a high-power, pulsed GaAlAs tapered amplifier seeded by an external-cavity diode laser. Pulsing the amplifier increased the 860 nm?215 nm conversion efficiency by 2 orders of magnitude with respect to cw operation. Detection of nitric oxide and sulfur dioxide by high-resolution absorption spectroscopy was demonstrated. PMID:18188256

  14. THE 217.5 nm BAND, INFRARED ABSORPTION, AND INFRARED EMISSION FEATURES IN HYDROGENATED AMORPHOUS CARBON NANOPARTICLES

    SciTech Connect

    Duley, W. W.; Hu, Anming E-mail: a2hu@uwaterloo.ca

    2012-12-20

    We report on the preparation of hydrogenated amorphous carbon nanoparticles whose spectral characteristics include an absorption band at 217.5 nm with the profile and characteristics of the interstellar 217.5 nm feature. Vibrational spectra of these particles also contain the features commonly observed in absorption and emission from dust in the diffuse interstellar medium. These materials are produced under ''slow'' deposition conditions by minimizing the flux of incident carbon atoms and by reducing surface mobility. The initial chemistry leads to the formation of carbon chains, together with a limited range of small aromatic ring molecules, and eventually results in carbon nanoparticles having an sp {sup 2}/sp {sup 3} ratio Almost-Equal-To 0.4. Spectroscopic analysis of particle composition indicates that naphthalene and naphthalene derivatives are important constituents of this material. We suggest that carbon nanoparticles with similar composition are responsible for the appearance of the interstellar 217.5 nm band and outline how these particles can form in situ under diffuse cloud conditions by deposition of carbon on the surface of silicate grains. Spectral data from carbon nanoparticles formed under these conditions accurately reproduce IR emission spectra from a number of Galactic sources. We provide the first detailed fits to observational spectra of Type A and B emission sources based entirely on measured spectra of a carbonaceous material that can be produced in the laboratory.

  15. Limitations and design considerations for donor–acceptor systems in luminescent solar concentrators: the effect of coupling-induced red-edge absorption

    NASA Astrophysics Data System (ADS)

    MacQueen, Rowan W.; Tayebjee, Murad J. Y.; Webb, James E. A.; Falber, Alexander; Thordarson, Pall; Schmidt, Timothy W.

    2016-06-01

    Luminescent solar concentrators (LSCs) use luminescence and waveguiding to concentrate photons within thin dielectric slabs for use in photovoltaic, lighting, and photobioreactor applications. Donor–acceptor systems of organic chromophores are widely used in LSCs to broaden the sunlight absorption range and attempt to reduce loss-inducing reabsorption by the emitting chromophore. We use raytrace simulations across a large parameter space to model the performance of LSCs containing two novel donor–acceptor trimers based on the perylene moiety. We find that under certain conditions, trimers outperform single-dye LSCs as expected. However, at higher concentrations, a slight increase in red-edge absorption by the trimers increases reabsorption and has a deleterious effect on LSC performance. This underscores the large effect that even small changes in the red edge can have, and may discourage the use of donor–acceptor schemes with high interchromophore coupling that promotes red-edge absorption. Finally, we show that for a LSC-PV pair, selecting a PV cell that is well-matched with the LSC emission spectrum has a large effect on the flux gain of the system, and that the systems studied here are well-matched to emerging PV technologies.

  16. Fluorinated graphene oxide for enhanced S and X-band microwave absorption

    NASA Astrophysics Data System (ADS)

    Sudeep, P. M.; Vinayasree, S.; Mohanan, P.; Ajayan, P. M.; Narayanan, T. N.; Anantharaman, M. R.

    2015-06-01

    Here we report the microwave absorbing properties of three graphene derivatives, namely, graphene oxide (GO), fluorinated GO (FGO, containing 5.6 at. % Fluorine (F)), and highly FGO (HFGO, containing 23 at. % F). FGO is known to be exhibiting improved electrochemical and electronic properties when compared to GO. Fluorination modifies the dielectric properties of GO and hence thought of as a good microwave absorber. The dielectric permittivities of GO, FGO, and HFGO were estimated in the S (2 GHz to 4 GHz) and X (8 GHz to 12 GHz) bands by employing cavity perturbation technique. For this, suspensions containing GO/FGO/HFGO were made in N-Methyl Pyrrolidone (NMP) and were subjected to cavity perturbation. The reflection loss was then estimated and it was found that -37 dB (at 3.2 GHz with 6.5 mm thickness) and -31 dB (at 2.8 GHz with 6 mm thickness) in the S band and a reflection loss of -18 dB (at 8.4 GHz with 2.5 mm thickness) and -10 dB (at 11 GHz with 2 mm thickness) in the X band were achieved for 0.01 wt. % of FGO and HFGO in NMP, respectively, suggesting that these materials can serve as efficient microwave absorbers even at low concentrations.

  17. Spectroscopic determination of leaf biochemistry using band-depth analysis of absorption features and stepwise multiple linear regression

    USGS Publications Warehouse

    Kokaly, R.F.; Clark, R.N.

    1999-01-01

    We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.30 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.We develop a new method for estimating the biochemistry of plant material using

  18. Topological band-order transition and quantum spin Hall edge engineering in functionalized X-Bi(111) (X = Ga, In, and Tl) bilayer.

    PubMed

    Kim, Youngjae; Yun, Won Seok; Lee, J D

    2016-01-01

    Functionalized X-Bi bilayers (X = Ga, In, and Tl) with halogens bonded on their both sides have been recently claimed to be the giant topological insulators due to the strong band inversion strengths. Employing the first-principles electronic structure calculation, we find the topological band order transition from the order p - p - s of the X-Bi bilayers with halogens on their both sides to the new order p - s - p of the bilayers (especially for X = Ga and In) with halogen on one side and hydrogen on the other side, where the asymmetric hydrogen bonding simulates the substrate. We further find that the p - s bulk band gap of the bilayer bearing the new order p - s - p sensitively depends on the electric field, which enables a meaningful engineering of the quantum spin Hall edge state by controlling the external electric field. PMID:27623710

  19. Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands

    SciTech Connect

    Zhang, J.H.; Ding, J.W.; Cao, J.X.; Zhang, Y.L.

    2011-03-15

    The formation energies, electronic structures and optical properties of TM:ZnS systems (TM=Cr{sup 2+}, Mn{sup 2+}, Fe{sup 2+}, Co{sup 2+} and Ni{sup 2+}) are investigated by using the first principles method. It is found that the wurtzite and zinc-blende structures have about the same stability, and thus can coexist in the TM:ZnS system. From the wurtzite TM:ZnS, especially, a partially filled intermediate band (IB) is obtained at TM=Cr{sup 2+}, Ni{sup 2+} and Fe{sup 2+}, while it is absent at TM=Mn{sup 2+} and Co{sup 2+}. The additional absorptions are obtained in infrared, visible and ultraviolet (UV) regions, due to the completely spin-polarized IB at Fermi level. The results are very helpful for both the designs and applications of TM:ZnS opto-electronics devices, such as solar-cell prototype. -- Graphical abstract: Absorption coefficients of w-TM{sub x}Zn{sub 1-x}S crystals (TM=Cr{sup 2+}, Mn{sup 2+}, Fe{sup 2+}, Co{sup 2+} and Ni{sup 2+}) at x=0.028. The results may be helpful for the design and applications of TM:ZnS devices, especially for the new high efficiency solar-cell prototype, UV detector and UV LEDs. Display Omitted Research highlights: > It is found that the wurtzite and zinc-blende structures can coexist in TM:ZnS. > An intermediate band is obtained in TM:ZnS at TM=Cr{sup 2+}, Ni{sup 2+} and Fe{sup 2+}. > The absorption coefficients are obtained in infrared, visible and ultraviolet regions.

  20. On the sub-band gap optical absorption in heat treated cadmium sulphide thin film deposited on glass by chemical bath deposition technique

    SciTech Connect

    Chattopadhyay, P.; Karim, B.; Guha Roy, S.

    2013-12-28

    The sub-band gap optical absorption in chemical bath deposited cadmium sulphide thin films annealed at different temperatures has been critically analyzed with special reference to Urbach relation. It has been found that the absorption co-efficient of the material in the sub-band gap region is nearly constant up to a certain critical value of the photon energy. However, as the photon energy exceeds the critical value, the absorption coefficient increases exponentially indicating the dominance of Urbach rule. The absorption coefficients in the constant absorption region and the Urbach region have been found to be sensitive to annealing temperature. A critical examination of the temperature dependence of the absorption coefficient indicates two different kinds of optical transitions to be operative in the sub-band gap region. After a careful analyses of SEM images, energy dispersive x-ray spectra, and the dc current-voltage characteristics, we conclude that the absorption spectra in the sub-band gap domain is possibly associated with optical transition processes involving deep levels and the grain boundary states of the material.

  1. Characterization of NH overtone and combination bands in the near-infrared absorption spectra of simple cyclic imides

    NASA Astrophysics Data System (ADS)

    McNeilly, Patrick J.; Andrea, Tariq A.; Krikorian, S. Edward

    1992-10-01

    Bands due to overtone and combination vibrational modes attributable to the imide grouping have been elucidated in the near-IR absorption spectra of small-ring cyclic imides, in which the grouping is in a cis, cis conformation. The spectra closely parallel the spectra of cis lactams except that two combination modes involving the carbonyl stretching fundamental, [ν(NH) + ν(CO)] and [2ν(C=O) + imide III], occur at higher wavenumbers in the imide spectra, reflecting the higher frequency at which this fundamental absorbs. This same factor results in a reversal in the wavenumber positions of the [2ν(CO) + imide III] and [ν(NH) + imide III] combination bands in the imide spectra relative to those in the lactam spectra. In addition, in-phase and out-of-phase vibrational coupling between the two carbonyl groups in the imides may compound the band due to the [ν(NH) + ν(CO)] combination mode. These three spectral characteristics serve to distinguish the imides from the lactams in the near-IR.

  2. Fluorinated graphene oxide for enhanced S and X-band microwave absorption

    SciTech Connect

    Sudeep, P. M.; Vinayasree, S.; Mohanan, P.; Ajayan, P. M.; Narayanan, T. N.; Anantharaman, M. R.

    2015-06-01

    Here we report the microwave absorbing properties of three graphene derivatives, namely, graphene oxide (GO), fluorinated GO (FGO, containing 5.6 at. % Fluorine (F)), and highly FGO (HFGO, containing 23 at. % F). FGO is known to be exhibiting improved electrochemical and electronic properties when compared to GO. Fluorination modifies the dielectric properties of GO and hence thought of as a good microwave absorber. The dielectric permittivities of GO, FGO, and HFGO were estimated in the S (2 GHz to 4 GHz) and X (8 GHz to 12 GHz) bands by employing cavity perturbation technique. For this, suspensions containing GO/FGO/HFGO were made in N-Methyl Pyrrolidone (NMP) and were subjected to cavity perturbation. The reflection loss was then estimated and it was found that −37 dB (at 3.2 GHz with 6.5 mm thickness) and −31 dB (at 2.8 GHz with 6 mm thickness) in the S band and a reflection loss of −18 dB (at 8.4 GHz with 2.5 mm thickness) and −10 dB (at 11 GHz with 2 mm thickness) in the X band were achieved for 0.01 wt. % of FGO and HFGO in NMP, respectively, suggesting that these materials can serve as efficient microwave absorbers even at low concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    1999-11-01

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

  4. Multilayer Cloud Detection with the MODIS Near-Infrared Water Vapor Absorption Band

    NASA Technical Reports Server (NTRS)

    Wind, Galina; Platnick, Steven; King, Michael D.; Hubanks, Paul A,; Pavolonis, Michael J.; Heidinger, Andrew K.; Yang, Ping; Baum, Bryan A.

    2009-01-01

    Data Collection 5 processing for the Moderate Resolution Imaging Spectroradiometer (MODIS) onboard the NASA Earth Observing System EOS Terra and Aqua spacecraft includes an algorithm for detecting multilayered clouds in daytime. The main objective of this algorithm is to detect multilayered cloud scenes, specifically optically thin ice cloud overlying a lower-level water cloud, that presents difficulties for retrieving cloud effective radius using single layer plane-parallel cloud models. The algorithm uses the MODIS 0.94 micron water vapor band along with CO2 bands to obtain two above-cloud precipitable water retrievals, the difference of which, in conjunction with additional tests, provides a map of where multilayered clouds might potentially exist. The presence of a multilayered cloud results in a large difference in retrievals of above-cloud properties between the CO2 and the 0.94 micron methods. In this paper the MODIS multilayered cloud algorithm is described, results of using the algorithm over example scenes are shown, and global statistics for multilayered clouds as observed by MODIS are discussed. A theoretical study of the algorithm behavior for simulated multilayered clouds is also given. Results are compared to two other comparable passive imager methods. A set of standard cloudy atmospheric profiles developed during the course of this investigation is also presented. The results lead to the conclusion that the MODIS multilayer cloud detection algorithm has some skill in identifying multilayered clouds with different thermodynamic phases

  5. Accurate determination of the valence band edge in hard x-ray photoemission spectra using GW theory

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Nemšák, Slavomír; Conti, Giuseppina; Gloskovskii, Andrei; Pálsson, Gunnar Karl; Schneider, Claus M.; Drube, Wolfgang; Louie, Steven G.; Fadley, Charles

    2016-04-01

    We introduce a new method for determining accurate values of the valence-band maximum in x-ray photoemission spectra. Specifically, we align the sharpest peak in the valence-band region of the experimental spectrum with the corresponding feature of a theoretical valence-band density of states curve from ab initio GW theory calculations. This method is particularly useful for soft and hard x-ray photoemission studies of materials with a mixture of valence-band characters, where strong matrix element effects can render standard methods for extracting the valence-band maximum unreliable. We apply our method to hydrogen-terminated boron-doped diamond, which is a promising substrate material for novel solar cell devices. By carrying out photoemission experiments with variable light polarizations, we verify the accuracy of our analysis and the general validity of the method.

  6. Efficacy of calcein and Coomassie Blue dyeing of shell growing-edges and micro growth-bands: ageing juvenile of Pinctada mazatlanica (Pterioida: Pteriidae).

    PubMed

    Loria, Patricia L McCoy; Huato-Soberanis, Leonardo

    2014-09-01

    Age validation is the first step to determine shellfish species age determination. This information is vital for different inferential models used in marine ecosystem management activities. In spite that various validation techniques are used for marking carbon calcium structures, the calcein marking technique for oysters had never been used for age validation in Pinctada mazatlanica. Thus the objectives of this study included: the evaluation of calcein to mark a shell growing-edge, and the efficacy of Coomassie Blue staining on posterior shell growth, to produce visible micro growth-bands that would enable age validation of juvenile mother-of-pearl oysters. Oysters were collected and cultivated at The Perlas del Cortez S. de R. L. MI. pearl-farming operation, in Pichilingue, La Paz Bay, Baja California Sur, Mexico; a total of 36 oysters (shell height 11.5-36.4 mm) were injected with calcein (0.125 g/L), and another 50 oysters (shell height 14.8-42.7 mm) were submersed in calcein (0.4 and 0.7 g/L). Shell slices of calcein-marked oysters were posteriourly stained with Coomassie Blue R-25 for micro growth-band recognition. Our results showed that Calcein marking only worked by submersion and produced a concise bright lime-green florescent band along the growing-edge with clear boundaries for both concentrations. However, marks resulted better at the lower calcein concentration (0.4 g/L) with more "perfect" and "good" marks on the growing-edge (p = 0.0012). Commassie Blue staining technique was successful, and allowed to conclude that one micro growth-band was laid down per day, similar to other oyster species. Mean 15-d increment of shell growth height was slightly greater at the lower calcein concentration (= 0.735 mm) than at the higher one (= 0.577 mm) (not significant difference, p = 0.198). Calcein marking of shell growing-edges and Commassie Blue staining of posterior shell growth, as a method for age validation is recommended for shellfish shell growth-band

  7. Ligand K-edge x-ray absorption spectroscopy as a probe of ligand-metal bonding: Charge donation and covalency in copper-chloride systems

    SciTech Connect

    Shadle, S.E.; Hedman, B.; Solomon, E.I.; Hodgson, K.O.

    1994-09-14

    X-ray absorption spectra (XAS) have been measured at the chloride K-edge for a series of complexes containing chloride ligands bound to open shell d{sup 9} copper ions in order to probe ligand-metal bonding. The intensity of the pre-edge feature in these spectra reflects the covalency in the half-occupied d{sub x}{sup 2-}{sub y}{sup 2-} derived molecular orbital (HOMO) of the complex. The energy of the pre-edge feature as well as the energy of the rising absorption edge provides quantitative information about the covalency of the ligand-metal interaction, the charge donated by the chloride, and the energy of the copper d-manifold. The results demonstrate that ligand K-edge XAS features can be used to obtain information about ligand-metal bonding. The results also identify the chemical basis for trends in the XAS data for the following complexes: D{sub 4h} CuCl{sub 4}{sup 2-}, D{sub 2d} CuCl{sub 4}{sup 2-}, planar trans-CuCl{sub 2-} (pdmp){sub 2} (pdmp = N-phenyl-3,5-dimethylpyrazole), square pyramidal CuCl{sub 5}{sup 3-}, the planar dimer KCuCl{sub 3}, the distorted tetrahedral dimer (Ph{sub 4}P)CuCl{sub 3}, and two dimers with mixed ligation, one containing a bridging chloride, and the other, containing terminally bound chloride. Several of these results are supported by independent spectral data or by basic ligand field concepts. A geometric distortion from square planar to distorted tetrahedral results in a decrease in the chloride-copper HOMO covalency but an increase in the total charge donation by the chlorides. While the geometry can maximize the overlap for a highly covalent HOMO, this does not necessarily reflect the overall charge donation.

  8. Near band-edge luminescence and evidence of the weakening of the N-conduction-band coupling for partially relaxed and high nitrogen composition GaAs1-xNx epilayers

    NASA Astrophysics Data System (ADS)

    Coaquira, J. A. H.; Pinault, M.-A.; Litvinchuk, A. P.; Bhusal, L.; Freundlich, Alex

    2007-10-01

    Photoluminescence and absorption spectroscopy experiments are implemented on as-grown and thermally annealed GaAs1-xNx epilayers grown on GaAs(001) having a nitrogen content in the range of 0.4%-7.1%. At low temperature, photoluminescence spectra exhibit two sets of features: (i) a relatively broad peak at low energy in the vicinity of the band gap predicted by the band anticrossing model (BAC) and (ii) sharp excitonic features at higher energy (over 100meV above the band gap for x >4%). An enhancement of the photoluminescence response of excitonic emissions and a notable intensity reduction of the deeper luminescence were systematically observed for samples subjected to high-temperature postgrowth annealing treatments. For pseudomorphically strained low nitrogen-containing epilayers (x<2%), and by taking into account the strain magnitude and the average substitutional nitrogen concentration (as extracted from x-ray analysis), excitonic energies and corresponding band gaps (as determined by absorption spectroscopy) are well described within the framework of the BAC model. The extracted binding energies of split heavy- and light-hole excitons are found to be consistent with the expected increase of electron effective masses. For thick partially relaxed epilayers (1%4%), the fundamental band gap of GaAsN is found at significantly higher energies than those predicted by the BAC model using the commonly accepted nitrogen coupling parameter CNM=2.7eV. To account, within the BAC framework, for the apparent deceleration in the band-gap reduction rate requires the use of a smaller coupling constant (CNM=2.0eV), which suggests a weakening of the strength of the interaction between the localized nitrogen state and the conduction band of the host matrix. This observation seems to be associated with the increasing population of N-related defects.

  9. The effect of film thickness on the optical absorption edge and optical constants of the Cr(III) organic thin films

    NASA Astrophysics Data System (ADS)

    Yakuphanoglu, F.; Sekerci, M.; Balaban, A.

    2005-05-01

    The effect of film thickness on optical properties of the Cr(III) complex having 2-pyridincarbaldehye thiosemicarbazone thin films was investigated. The analyses of the optical absorption data revealed existence of direct and indirect transitions in the optical band gap. The optical constants (refractive index and dielectric constant) of the thin films were determined. The thickness of the films causes important changes in refractive index and real part-imaginary parts of the dielectric constant. The most significant result of the present study is to indicate that thickness of the film can be used to modify in the optical band gaps and optical constant of the thin films.

  10. Jupiter's atmospheric composition and cloud structure deduced from absorption bands in reflected sunlight

    NASA Technical Reports Server (NTRS)

    Sato, M.; Hansen, J. E.

    1979-01-01

    The spectrum of sunlight reflected by Jupiter is analyzed by comparing observations of Woodman (1979) with multiple-scattering computations. The analysis yields information on the vertical cloud structure at several latitudes and on the abundance of CH4 and NH3 in the atmosphere of Jupiter. The abundances of CH4 and NH3 suggest that all ices and rocks are overabundant on Jupiter by a factor of 2 or more, providing an important constraint on models for the formation of Jupiter from the primitive solar nebula. The pressure level of the clouds, the gaseous NH3 abundance, the mean temperature profile, and the Clausius-Clapeyron relation suggest that these clouds are predominantly ammonia crystals with the cloud bottom at 600-700 mb. A diffuse distribution of aerosols exists between 150 and 500 mb, and the spectral variation of albedo reflects a changing bulk absorption coefficient of the material composing the aerosols and is diagnostic of the aerosol composition.

  11. Transient magneto-photoinduced absorption study of singlet fission in low band gap copolymers

    NASA Astrophysics Data System (ADS)

    Huynh, Uyen; Vardeny, Z. Valy

    2015-03-01

    We have observed the existence of singlet fission in thin films of low band gap (LBG) copolymers, PDTP-DFBT and PTB7, using the ultrafast optical pump/probe spectroscopy, probed at the energy range from IR to MIR. The singlet fission is the dissociation of a singlet exciton into two triplets through an intermediate triplet pair state (TT pair) in an overall singlet configuration; in the studied copolymers, it was observed to be very fast, in femtosecond time domain. The intermediate TT state, which dissociates into two separated triplets at later time, or recombines to the ground state appears instantaneously with the singlet exciton formation using our laser system that has ~ 150 fs time resolution. The interplay between the rate of singlet fission into sTT pairs, triplet fusion back to singlet excitons and relaxation between the TT spin sublevels explains the obtained opposite pattern of the transient magnetic field response on the dynamics of singlet excitons and TT pairs.

  12. Evidence for a defect level above the conduction band edge of InAs/InAsSb type-II superlattices for applications in efficient infrared photodetectors

    SciTech Connect

    Prins, A. D.; Lewis, M. K.; Bushell, Z. L.; Sweeney, S. J.; Liu, S.; Zhang, Y.-H.

    2015-04-27

    We report pressure-dependent photoluminescence (PL) experiments under hydrostatic pressures up to 2.16 GPa on a mid-wave infrared InAs/InAs{sub 0.86}Sb{sub 0.14} type-II superlattice (T2SL) structure at different pump laser excitation powers and sample temperatures. The pressure coefficient of the T2SL transition was found to be 93 ± 2 meV·GPa{sup −1}. The integrated PL intensity increases with pressure up to 1.9 GPa then quenches rapidly indicating a pressure induced level crossing with the conduction band states at ∼2 GPa. Analysis of the PL intensity as a function of excitation power at 0, 0.42, 1.87, and 2.16 GPa shows a clear change in the dominant photo-generated carrier recombination mechanism from radiative to defect related. From these data, evidence for a defect level situated at 0.18 ± 0.01 eV above the conduction band edge of InAs at ambient pressure is presented. This assumes a pressure-dependent energy shift of −11 meV·GPa{sup −1} for the valence band edge and that the defect level is insensitive to pressure, both of which are supported by an Arrhenius activation energy analysis.

  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. PMID:23360082

  14. Depolarisation of light scattered by disperse systems of low-dimensional potassium polytitanate nanoparticles in the fundamental absorption band

    SciTech Connect

    Zimnyakov, D A; Yuvchenko, S A; Pravdin, A B; Kochubey, V I; Gorokhovsky, A V; Tretyachenko, E V; Kunitsky, A I

    2014-07-31

    The results of experimental studies of depolarising properties of disperse systems on the basis of potassium polytitanate nanoplatelets and nanoribbons in the visible and near-UV spectral regions are presented. It is shown that in the fundamental absorption band of the nanoparticle material the increase in the depolarisation factor takes place for the radiation scattered perpendicularly to the direction of the probing beam. For nanoribbons a pronounced peak of depolarisation is observed, which is caused by the essential anisotropy of the particles shape and the peculiarities of the behaviour of the material dielectric function. The empirical data are compared with the theoretical results for 'nanodiscs' and 'nanoneedles' with the model dielectric function, corresponding to that obtained from optical constants of the titanium dioxide dielectric function. (laser biophotonics)

  15. Preparation of Ni-B Coating on Carbonyl Iron and Its Microwave Absorption Properties in the X Band

    NASA Astrophysics Data System (ADS)

    Li, Rong; Zhou, Wan-Cheng; Qing, Yu-Chang

    2014-09-01

    Ni-B coated carbonyl iron particles (CI@Ni-B) are prepared by the electroless plating technique. The structure, morphology, and antioxidant properties of the CI@Ni-B particles are analyzed. The results demonstrate that the CI particles have been coated with intact spherical-shell Ni-B coating, indicating the core-shell structure of CI@Ni-B particles, and the Ni-B coating can prevent the further oxidation of the CI particles. Compared with the raw CI particles/paraffin coatings with the same coating thickness of 2.0 mm and particles content of 70%, the CI@Ni-B particles/paraffin coatings possess higher microwave absorption (the RL exceeding -10 dB is obtained in the whole X band (8.2-12.4 GHz) with minimal RL of -35.0 dB at 9.2 GHz).

  16. A model for the spectral dependence of optically induced absorption in amorphous silicon

    NASA Technical Reports Server (NTRS)

    Lawandy, N. M.

    1990-01-01

    A model based on transitions from localized band tail states to states above the mobility edge is used to explain the broad band induced absorptions observed in recent pump-probe experiments. The model gives the observed decrease of absorption with frequency at subband gap photo energies and high carrier densities (of about 10 to the 20th/cu cm). At lower carrier densities, the absorption has a maximun which is sensitive to the spatial extent of the band tail states.

  17. Infrared absorption band and vibronic structure of the nitrogen-vacancy center in diamond

    NASA Astrophysics Data System (ADS)

    Kehayias, P.; Doherty, M. W.; English, D.; Fischer, R.; Jarmola, A.; Jensen, K.; Leefer, N.; Hemmer, P.; Manson, N. B.; Budker, D.

    2013-10-01

    Negatively charged nitrogen-vacancy (NV-) color centers in diamond have generated much interest for use in quantum technology. Despite the progress made in developing their applications, many questions about the basic properties of NV- centers remain unresolved. Understanding these properties can validate theoretical models of NV-, improve their use in applications, and support their development into competitive quantum devices. In particular, knowledge of the phonon modes of the 1A1 electronic state is key for understanding the optical pumping process. Using pump-probe spectroscopy, we measured the phonon sideband of the 1E→1A1 electronic transition in the NV- center. From this we calculated the 1E→1A1 one-phonon absorption spectrum and found it to differ from that of the 3E→3A2 transition, a result which is not anticipated by previous group-theoretical models of the NV- electronic states. We identified a high-energy 169-meV localized phonon mode of the 1A1 level.

  18. The C 1s and N 1s near edge x-ray absorption fine structure spectra of five azabenzenes in the gas phase.

    PubMed

    Vall-llosera, G; Gao, B; Kivimäki, A; Coreno, M; Alvarez Ruiz, J; de Simone, M; Agren, H; Rachlew, E

    2008-01-28

    Near edge x-ray absorption fine structure spectra have been measured and interpreted by means of density functional theory for five different azabenzenes (pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine) in the gas phase. The experimental and theoretical spectra at the N 1s and C 1s edges show a strong resonance assigned to the transition of the 1s electron in the respective N or C atoms to the lowest unoccupied molecular orbital with pi(*) symmetry. As opposed to the N 1s edge, at the C 1s edge this resonance is split due to the different environments of the core hole atom in the molecule. The shift in atomic core-level energy due to a specific chemical environment is explained with the higher electronegativity of the N atom compared to the C atom. The remaining resonances below the ionization potential (IP) are assigned to sigma or pi [corrected] orbitals with mixed valence/Rydberg [corrected] character. Upon N addition, a reduction of intensity is observed in the Rydberg region at both edges as compared to the intensity in the continuum. Above the IP one or more resonances are seen and ascribed here to transitions to sigma(*) orbitals. Calculating the experimental and theoretical Delta(pi) term values at both edges, we observe that they are almost the same within +/-1 eV as expected for isoelectronic bonded pairs. The term values of the pi(*) and sigma(*) resonances are discussed in terms of the total Z number of the atoms participating in the bond. PMID:18247958

  19. Formation of an SEI on a LiMn(2)O(4) Cathode during Room Temperature Charge-Discharge Cycling Studied by Soft X-Ray Absorption Spectroscopy at the Fluorine K-edge

    SciTech Connect

    Chung, K.Y.; Yang, X.; Yoon, W.-S.; Kim, K.-B.; Cho, B.-W.

    2011-11-01

    The solid electrolyte interface (SEI) formation on the surface of LiMn{sub 2}O{sub 4} electrodes during room temperature charge-discharge cycling was studied using soft X-ray absorption spectroscopy at the Fluorine (F) K-edge. LiMn{sub 2}O{sub 4} electrodes without any binder were prepared by electrostatic spray deposition to eliminate the signal originating from the PVDF binder in the F K-edge X-ray absorption spectra. The F K-edge absorption spectra show that the SEI layer forms at a very early stage of cycling. SEI growth takes place during discharge. In addition, LiF formation is accelerated if the discharge step follows a charge step. The F K-edge absorption spectra suggest that the major component of the SEI is LiF.

  20. Experimental and theoretical comparison between absorption, total electron yield, and fluorescence spectra of rare-earth M{sub 5} edges

    SciTech Connect

    Pompa, M.; Flank, A.M.; Lagarde, P.; Rife, J.C.; Stekhin, I.; Nakazawa, M.; Ogasawara, H.; Kotani, A.

    1997-07-01

    Besides the now well-known self-absorption effect, several phenomena related to the multiplet structure of the intermediate state may occur which render x-ray fluorescence different from the true absorption in 3d transition metals at the L edge and at the M{sub 4,5} edges of rare earths. Special selection rules of the radiative de-excitation process play an important role there. We have measured the absorption coefficient of thin films of lanthanum, samarium, and thulium deposited on an aluminum foil, at room temperature, through the simultaneous detection of the transmission, total electron yield, and 150-eV bandwidth fluorescence yield. The latter result shows differences as compared to the other two, and exhibits polarization effects depending upon the angle between incident and outgoing photons. The resonant x-ray fluorescence spectrum is calculated using an atomic model, and then integrated over the emitted energy, to predict the fluorescence yield spectrum. Very good agreement is obtained between the theory and experiment. {copyright} {ital 1997} {ital The American Physical Society}

  1. Intervalence-Band Absorption Saturation And Optically Induced Damage Of GaAs By Pulsed CO2 Laser Radiation

    NASA Astrophysics Data System (ADS)

    James, R. B.; Christie, W. H.; Eby, R. E.; Darken, L. S.; Mills, B. E.

    1985-11-01

    The absorption of CO2, laser radiation in p-type GaAs is dominated by direct free-hole transitions between states in the heavy- and light-hole bands. For laser intensities on the order of 10 MW/cm2, the absorption associated with these transitions in moderately Zn-doped GaAs begins to saturate in a manner predicted by an inhomogeneously broadened two-level model. For heavily Zn-doped samples (>1018 cm -3), large areas of the surface are found to melt at comparable laser energy densities, in contrast to the lightly doped samples in which the damage initially occurs in small localized sites. As the energy density of the CO2 laser radiation is progressively increased, the surface topography of the samples shows signs of ripple patterns, high local stress, vaporization of material, and exfoliation of solid GaAs fragments. X-ray emission data taken on the laser-melted samples show that there is a loss of As, compared to Ga, from the surface during the high temperature cycling. Secondary ion mass spectrometry (SIMS) measurements are used to study the diffusion of oxygen from the native oxide and the incorporation of trapped oxygen in the near-surface region of the GaAs samples that have been melted by a CO2 laser pulse. We find that oxygen trapping does occur, and that the amount and depth of the oxygen signal depends on the laser energy density and number of laser shots.

  2. Photodissociation of water in the first absorption band: A prototype for dissociation on a repulsive potential energy surface

    SciTech Connect

    Engel, V.; Staemmler, V.; Vander Wal, R.L.; Crim, F.F.

    1992-04-16

    The photodissociation of water in the first absorption band, H{sub 2}O(X) + {Dirac_h}{omega} {yields} H{sub 2}O(A{sup 1}B{sub 1}) {yields} H({sup 2}S) + OH({sup 2}II), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives-absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the A state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface. 80 refs., 14 figs.

  3. Observations of an intense field-aligned thermal ion flow and associated intense narrow band electric field oscillations. [at auroral arc edge

    NASA Technical Reports Server (NTRS)

    Bering, E. A.; Kelley, M. C.; Mozer, F. S.

    1975-01-01

    An investigation is conducted concerning the conditions encountered during a Javelin sounding rocket experiment conducted on Apr. 3, 1970 at Fort Churchill, Canada. Evidence is presented that near the equatorward edge of the auroral arc an intense beam of cold plasma ions was flowing parallel to the earth's magnetic field. The beam was associated with intense narrow band electric field oscillations near the local ion gyrofrequency. The data support the hypothesis that intense electrostatic ion cyclotron waves were driven unstable by field-aligned currents.

  4. Variation of band-edge position with errors in the monitoring of layer termination level for long- and short-wave pass filters.

    PubMed

    Willey, R R; Machado, D E

    1999-09-01

    Optical monitoring of periodic thin-film stacks by the termination of each layer at the same constant photometric level has certain advantages. One of these principal advantages is the error compensation effect in the vicinity of the monitoring wavelength. In this study, we examine, by simulation, the effect of an error in the knowledge of the absolute value of the photometric termination level on the probable stability in the manufacture of the edge position of a blocked band. The results include equations that allow the determination of the appropriate values of parameters associated with the optimum termination levels to minimize the effects of such errors. PMID:18324052

  5. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    PubMed

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-01

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  6. The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Zander, R.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Grunson, M. R.; Farmer, C. B.

    1991-01-01

    The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

  7. Nonlinear polarization spectroscopy in the frequency domain of light-harvesting complex II: absorption band substructure and exciton dynamics.

    PubMed Central

    Lokstein, H; Leupold, D; Voigt, B; Nowak, F; Ehlert, J; Hoffmann, P; Garab, G

    1995-01-01

    Spectral substructure and ultrafast excitation dynamics have been investigated in the chlorophyll (Chl) a and b Qy region of isolated plant light-harvesting complex II (LHC II). We demonstrate the feasibility of Nonlinear Polarization Spectroscopy in the frequency domain, a novel photosynthesis research laser spectroscopic technique, to determine not only ultrafast population relaxation (T1) and dephasing (T2) times, but also to reveal the complex spectral substructure in the Qy band as well as the mode(s) of absorption band broadening at room temperature (RT). The study gives further direct evidence for the existence of up to now hypothetical "Chl forms". Of particular interest is the differentiated participation of the Chl forms in energy transfer in trimeric and aggregated LHC II. Limits for T2 are given in the range of a few ten fs. Inhomogeneous broadening does not exceed the homogeneous widths of the subbands at RT. The implications of the results for the energy transfer mechanisms in the antenna are discussed. PMID:8534824

  8. Visible-band (390-940nm) monitoring of the Pluto absorption spectrum during the New Horizons encounter

    NASA Astrophysics Data System (ADS)

    Smith, Robert J.; Marchant, Jonathan M.

    2015-11-01

    Whilst Earth-based observations obviously cannot compete with New Horizons’ on-board instrumentation in most regards, the New Horizons data set is essentially a snapshot of Pluto in July 2015. The New Horizons project team therefore coordinated a broad international observing campaign to provide temporal context and to take advantage of the once-in-a-lifetime opportunity to directly link our Earth-based view of Pluto with “ground truth” provided by in situ measurements. This both adds value to existing archival data sets and forms the basis of long term, monitoring as we watch Pluto recede from the Sun over the coming years. We present visible-band (390-940nm) monitoring of the Pluto absorption spectrum over the period July - October 2015 from the Liverpool Telescope (LT). In particular we wished to understand the well-known 6-day fluctuation in the methane ice absorption spectrum which is observable from Earth in relation to the never-before-available high resolution maps of the Pluto surface. The LT is a fully robotic 2.0m optical telescope that automatically and dynamically schedules observations across 30+ observing programmes with a broad instrument suite. It is ideal for both reactive response to dynamic events (such as the fly-by) and long term, stable monitoring with timing constraints individually optimised to the science requirements of each programme. For example past studies of the observed CH4 absorption variability have yielded ambiguity of whether they were caused by real physical changes or geometric observation constraints, in large part because of the uneven time sampling imposed by traditional telescope scheduling.

  9. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  10. Strained band edge characteristics from hybrid density functional theory and empirical pseudopotentials: GaAs, GaSb, InAs and InSb

    NASA Astrophysics Data System (ADS)

    Çakan, Aslı; Sevik, Cem; Bulutay, Ceyhun

    2016-03-01

    The properties of a semiconductor are drastically modified when the crystal point group symmetry is broken under an arbitrary strain. We investigate the family of semiconductors consisting of GaAs, GaSb, InAs and InSb, considering their electronic band structure and deformation potentials subject to various strains based on hybrid density functional theory. Guided by these first-principles results, we develop strain-compliant local pseudopotentials for use in the empirical pseudopotential method (EPM). We demonstrate that the newly proposed empirical pseudopotentials perform well close to band edges and under anisotropic crystal deformations. Using the EPM, we explore the heavy hole-light hole mixing characteristics under different stress directions, which may be useful in manipulating their transport properties and optical selection rules. The very low 5 Ry cutoff targeted in the generated pseudopotentials paves the way for large-scale EPM-based electronic structure computations involving these lattice mismatched constituents.

  11. Time-resolved near-edge x-ray absorption fine structure spectroscopy on photo-induced phase transitions using a tabletop soft-x-ray spectrometer

    NASA Astrophysics Data System (ADS)

    Grossmann, P.; Rajkovic, I.; Moré, R.; Norpoth, J.; Techert, S.; Jooss, C.; Mann, Klaus

    2012-05-01

    We present a table-top soft-x-ray spectrometer for the wavelength range λ = 1-5 nm based on a stable laser-driven x-ray source, making use of a gas-puff target. With this setup, optical light-pump/soft-x-ray probe near-edge x-ray absorption fine structure (NEXAFS) experiments with a temporal resolution of about 230 ps are feasible. Pump-probe NEXAFS measurements were carried out in the "water-window" region (2.28 nm-4.36 nm) on the manganite Pr0.7Ca0.3MnO3, investigating diminutive changes of the oxygen K edge that derive from an optically induced phase transition. The results show the practicability of the table-top soft-x-ray spectrometer on demanding investigations so far exclusively conducted at synchrotron radiation sources.

  12. Percolative superconductivity in La{sub 2}CuO{sub 4.06} by lattice granularity patterns with scanning micro x-ray absorption near edge structure

    SciTech Connect

    Poccia, Nicola; Chorro, Matthieu; Ricci, Alessandro; Xu, Wei; Marcelli, Augusto; Campi, Gaetano; Bianconi, Antonio

    2014-06-02

    The simplest cuprate superconductor La{sub 2}CuO{sub 4+y} with mobile oxygen interstitials exhibits a clear phase separation. It is known that oxygen interstitials enter into the rocksalt La{sub 2}O{sub 2+y} spacer layers forming oxygen interstitials rich puddles and poor puddles but only recently a bulk multiscale structural phase separation has been observed by using scanning micro X-ray diffraction. Here we get further information on their spatial distribution, using scanning La L{sub 3}-edge micro X-ray absorption near edge structure. Percolating networks of oxygen rich puddles are observed in different micrometer size portions of the crystals. Moreover, the complex surface resistivity shows two jumps associated to the onset of intra-puddle and inter-puddles percolative superconductivity. The similarity of oxygen doped La{sub 2}CuO{sub 4+y}, with the well established phase separation in iron selenide superconductors is also discussed.

  13. The origin of luminescence from di[4-(4-diphenylaminophenyl)phenyl]sulfone (DAPSF), a blue light emitter: an X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study.

    PubMed

    Zhang, Duo; Zhang, Hui; Zhang, Xiaohong; Sham, Tsun-Kong; Hu, Yongfeng; Sun, Xuhui

    2016-02-24

    The electronic structure and optical properties of di[4-(4-diphenylaminophenyl)phenyl]sulfone (denoted as DAPSF), a highly efficient fluorophor, have been investigated using X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) spectroscopy at excitation energies across the C, N, O K-edges and the sulfur K-edge. The results indicate that the blue luminescence is mainly related to the sulfur functional group. PMID:26866785

  14. Tunable Q-switched fiber laser based on saturable edge-state absorption in few-layer molybdenum disulfide (MoS₂).

    PubMed

    Woodward, R I; Kelleher, E J R; Howe, R C T; Hu, G; Torrisi, F; Hasan, T; Popov, S V; Taylor, J R

    2014-12-15

    We fabricate a few-layer molybdenum disulfide (MoS₂) polymer composite saturable absorber by liquid-phase exfoliation, and use this to passively Q-switch an ytterbium-doped fiber laser, tunable from 1030 to 1070 nm. Self-starting Q-switching generates 2.88 μs pulses at 74 kHz repetition rate, with over 100 nJ pulse energy. We propose a mechanism, based on edge states within the bandgap, responsible for the wideband nonlinear optical absorption exhibited by our few-layer MoS₂ sample, despite operating at photon energies lower than the material bandgap. PMID:25607060

  15. Mechanism of the CO oxidation reaction on O-precovered Pt(111) surfaces studied with near-edge x-ray absorption fine structure spectroscopy

    SciTech Connect

    Nakai, I.; Kondoh, H.; Amemiya, K.; Nagasaka, M.; Shimada, T.; Yokota, R.; Nambu, A.; Ohta, T.

    2005-04-01

    The mechanism of CO oxidation reaction on oxygen-precovered Pt(111) surfaces has been studied by using time-resolved near-edge x-ray absorption fine structure spectroscopy. The whole reaction process is composed of two distinct paths: (1) a reaction of isolated oxygen atoms with adsorbed CO, and (2) a reaction of island-periphery oxygen atoms after the CO saturation. CO coadsorption plays a role to induce the dynamic change in spatial distribution of O atoms, which switches over the two reaction paths. These mechanisms were confirmed by kinetic Monte Carlo simulations. The effect of coadsorbed water in the reaction mechanism was also examined.

  16. C 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) of substituted benzoic acids: a theoretical and experimental study

    SciTech Connect

    Baldea,I.; Schimmelpfennig, B.; Plaschke, M.; Rothe, J.; Schirmer, J.; Trofimov, A.; Fanghaenel, T.

    2007-01-01

    Ab initio calculations are performed to explain the discrete transitions in experimental C 1s-NEXAFS (near edge X-ray absorption fine structure) spectra of various benzoic acid derivates. Transition energies and oscillator strengths of the contributing C 1s-{pi}* excitations are computed using the ADC(2) (second-order algebraic-diagrammatic construction) method. This method is demonstrated to be well suited for the finite electronic systems represented by these simple organic acids. There is good agreement between experiment and theory reproducing all the relevant spectral features. Some transitions can only be assigned based on a theoretical foundation. Remaining discrepancies between experimental and computed spectra are discussed.

  17. Unraveling the Solid-Liquid-Vapor Phase Transition Dynamics at the Atomic Level with Ultrafast X-Ray Absorption Near-Edge Spectroscopy

    NASA Astrophysics Data System (ADS)

    Dorchies, F.; Lévy, A.; Goyon, C.; Combis, P.; Descamps, D.; Fourment, C.; Harmand, M.; Hulin, S.; Leguay, P. M.; Petit, S.; Peyrusse, O.; Santos, J. J.

    2011-12-01

    X-ray absorption near-edge spectroscopy (XANES) is a powerful probe of electronic and atomic structures in various media, ranging from molecules to condensed matter. We show how ultrafast time resolution opens new possibilities to investigate highly nonequilibrium states of matter including phase transitions. Based on a tabletop laser-plasma ultrafast x-ray source, we have performed a time-resolved (˜3ps) XANES experiment that reveals the evolution of an aluminum foil at the atomic level, when undergoing ultrafast laser heating and ablation. X-ray absorption spectra highlight an ultrafast transition from the crystalline solid to the disordered liquid followed by a progressive transition of the delocalized valence electronic structure (metal) down to localized atomic orbitals (nonmetal—vapor), as the average distance between atoms increases.

  18. Atomic Resolution Mapping of the Excited-State Electronic Structure of Cu2O with Time-Resolved X-Ray Absorption Spectroscopy

    SciTech Connect

    Hillyard, Patrick B.; Kuchibhatla, Satyanarayana V N T; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, Ponnusamy; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Gaffney, Kelly J.

    2009-09-29

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that that the conduction band and valence band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  19. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, Nils; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2010-05-02

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  20. 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. PMID:26742851

  1. Can We Afford These Affordances? GarageBand and the Double-Edged Sword of the Digital Audio Workstation

    ERIC Educational Resources Information Center

    Bell, Adam Patrick

    2015-01-01

    The proliferation of computers, tablets, and smartphones has resulted in digital audio workstations (DAWs) such as GarageBand in being some of the most widely distributed musical instruments. Positing that software designers are dictating the music education of DAW-dependent music-makers, I examine the fallacy that music-making applications such…

  2. Surface passivation of a photonic crystal band-edge laser by atomic layer deposition of SiO2 and its application for biosensing

    NASA Astrophysics Data System (ADS)

    Cha, Hyungrae; Lee, Jeongkug; Jordan, Luke R.; Lee, Si Hoon; Oh, Sang-Hyun; Kim, Hyo Jin; Park, Juhun; Hong, Seunghun; Jeon, Heonsu

    2015-02-01

    We report on the conformal surface passivation of photonic crystal (PC) laser devices with an ultrathin dielectric layer. Air-bridge-type Γ-point band-edge lasers (BELs) are fabricated by forming a honeycomb lattice two-dimensional PC structure into an InGaAsP multiple-quantum-well epilayer. Atomic layer deposition (ALD) is employed for conformal deposition of a few-nanometer-thick SiO2 layer over the entire device surface, not only on the top and bottom surfaces of the air-bridge membrane but also on the air-hole sidewalls. Despite its extreme thinness, the ALD passivation layer is found to protect the InGaAsP BEL devices from harsh chemicals. In addition, the ALD-SiO2 is compatible with the silane-based surface chemistry, which allows us to use ALD-passivated BEL devices as label-free biosensors. The standard streptavidin-biotin interaction shifts the BEL lasing wavelength by ~1 nm for the dipole-like Γ-point band-edge mode. A sharp lasing line (<0.2 nm, full width at half-maximum) and a large refractive index sensitivity (~163 nm per RIU) produce a figure of merit as high as ~800 for our BEL biosensor, which is at least an order of magnitude higher than those of more common biosensors that rely on a broad resonance peak, showing that our nanolaser structures are suitable for highly sensitive biosensor applications.

  3. Identification of B-K near edge x-ray absorption fine structure peaks of boron nitride thin films prepared by sputtering deposition

    SciTech Connect

    Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru; Mochiji, Kozo

    2010-09-15

    Four {pi}{sup *} resonance peaks were observed in the B-K near edge x-ray absorption fine structure spectra of boron nitride thin films prepared by magnetron sputtering. In the past, these peaks have been explained as the K-absorption of boron atoms, which are present in environment containing nitrogen vacancies, the number of which is 1-3 corresponding to the three peaks at higher photon energy. However, the authors found that there was a strong correlation between the intensities of these three peaks and that of O-K absorption after wide range scanning and simultaneous measurement of nitrogen and oxygen K-absorptions of the BN films. Therefore, the authors conclude that these three peaks at the higher energy side correspond to boron atoms bound to one-to-three oxygen atoms instead of three nitrogen atoms surrounding the boron atom in the h-BN structure. The result of the first-principles calculation with a simple cluster model supported the validity of this explanation.

  4. Femtosecond probe-probe transmission studies of LT-grown GaAs near the band edge

    SciTech Connect

    Radousky, H.B.; Bello, A.F.; Erskine, D.J.; Dinh, L.N.; Bennahmias, M.J.; Perry, M.D.; Ditmire, T.R.; Mariella, R.P. Jr.

    1993-12-01

    We have studied the near-edge optical response of a LT-grown GaAs sample which was deposited at 300{degrees}C on a Si substrate, and then annealed at 600{degrees}C. The Si was etched away to leave a 1 micron free standing GaAs film. Femtosecond transmission measurements were made using an equal pulse technique at four wavelengths between 825 and 870 nm. For each wavelength we observe both a multipicosecond relaxation time, as well as a shorter relaxation time which is less than 100 femtoseconds.

  5. Differential analysis of band-edge photoluminescence spectra of germanium single crystals with different orientations under biaxial tensile strains

    NASA Astrophysics Data System (ADS)

    Emel'yanov, A. M.

    2016-06-01

    The previously published photoluminescence spectra of bulk germanium single crystals with orientations (100), (110), and (111) under different biaxial tensile strains have been investigated using the differential method proposed by the author for the analysis of luminescence spectra of semiconductors. An increase in the strain for all these orientations of the single crystals leads to a shift in the maxima of the differential spectra in the region of direct radiative transitions toward lower photon energies due to the narrowing of the germanium direct band gap. At the same time, the positions of the maxima of the differential spectra in the region of indirect radiative transitions remain almost unchanged. This indicates that the germanium indirect band gap does not depend on the tensile strains, at least for their values of ˜0.2-0.3%.

  6. Fabrication of multilayer mirrors consisting of oxide and nitride layers for continual use across the K-absorption edge of carbon.

    PubMed

    Ishino, Masahiko; Yoda, Osamu

    2004-03-20

    The development of multilayer mirrors for continual use around the K-absorption edge of carbon (4.4 nm) has been begun. Cobalt oxide (Co3O4), silicon oxide (SiO2), and boron nitride (BN) are found to be suitable for multilayer mirrors on the basis of theoretical calculations for wavelengths around the carbon K-absorption edge region. X-ray reflectivity curves with CuKalpha1 x rays of the fabricated Co3O4/SiO2 multilayers have sharp Bragg peaks, and the layer structures evaluated from transmission electron microscopy (TEM) observations are uniform. On the other hand, the Bragg peaks of Co3O4/BN multilayers split, and aggregated Co3O4 is observed. To improve the Co3O4 layer structure, chromium oxide (Cr2O3) was mixed into Co3O4. The mixed oxide layer structure in the Mix/BN multilayer (Mix = Co3O4 + Cr2O3) is relatively uniform, and the Bragg peaks do not split. PMID:15065714

  7. Theoretical X-ray production cross sections at incident photon energies across L{sub i} (i=1-3) absorption edges of Br

    SciTech Connect

    Puri, Sanjiv

    2015-08-28

    The X-ray production (XRP) cross sections, σ{sub Lk} (k = l, η, α, β{sub 6}, β{sub 1}, β{sub 3}, β{sub 4}, β{sub 9,10}, γ{sub 1,5}, γ{sub 2,3}) have been evaluated at incident photon energies across the L{sub i}(i=1-3) absorption edge energies of {sub 35}Br using theoretical data sets of different physical parameters, namely, the L{sub i}(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, in order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.

  8. X-ray Absorption Spectroscopy at the Sulfur K-Edge: A New Tool to Investigate the Biochemical Mechanisms of Neurodegeneration

    PubMed Central

    2012-01-01

    Sulfur containing molecules such as thiols, disulfides, sulfoxides, sulfonic acids, and sulfates may contribute to neurodegenerative processes. However, previous study in this field has been limited by the lack of in situ analytical techniques. This limitation may now be largely overcome following the development of synchrotron radiation X-ray absorption spectroscopy at the sulfur K-edge, which has been validated as a novel tool to investigate and image the speciation of sulfur in situ. In this investigation, we build the foundation required for future application of this technique to study and image the speciation of sulfur in situ within brain tissue. This study has determined the effect of sample preparation and fixation methods on the speciation of sulfur in thin sections of rat brain tissue, determined the speciation of sulfur within specific brain regions (brain stem and cerebellum), and identified sulfur specific markers of peroxidative stress following metal catalyzed reactive oxygen species production. X-ray absorption spectroscopy at the sulfur K-edge is now poised for an exciting new range of applications to study thiol redox, methionine oxidation, and the role of taurine and sulfatides during neurodegeneration. PMID:22860187

  9. Hybrid organic/inorganic band-edge modulation of p-Si(111) photoelectrodes: effects of R, metal oxide, and Pt on H2 generation.

    PubMed

    Seo, Junhyeok; Kim, Hark Jin; Pekarek, Ryan T; Rose, Michael J

    2015-03-11

    The efficient generation of dihydrogen on molecularly modified p-Si(111) has remained a challenge due to the low barrier heights observed on such surfaces. The band-edge and barrier height challenge is a primary obstruction to progress in the area of integration of molecular H2 electrocatalysts with silicon photoelectrodes. In this work, we demonstrate that an optimal combination of organic passivating agent and inorganic metal oxide leads to H2 evolution at photovoltages positive of RHE. Modulation of the passivating R group [CH3 → Ph → Naph → Anth → Ph(OMe)2] improves both the band-edge position and ΔV (Vonset - VJmax). Subsequent atomic layer deposition (ALD) of Al2O3 or TiO2 along with ALD-Pt deposition results in to our knowledge the first example of a positive H2 operating potential on molecularly modified Si(111). Mott-Schottky analyses reveal that the flat-band potential of the stable Ph(OMe)2 surface approaches that of the native (but unstable) hydride-terminated surface. The series resistance is diminished by the methoxy functional groups on the phenyl unit, due to its chemical and electronic connectivity with the TiO2 layer. Overall, judicious choice of the R group in conjunction with TiO2|Pt effects H2 generation on p-Si(111) photoelectrodes (Voc = 207 ± 5.2 mV; Jsc = -21.7 mA/cm(2); ff = 0.22; ηH2 = 0.99%). These results provide a viable hybrid strategy toward the operation of catalysts on molecularly modified p-Si(111). PMID:25716423

  10. Photoreflectance study of the near-band-edge transitions of chemical vapor deposition-grown mono- and few-layer MoS2 films

    NASA Astrophysics Data System (ADS)

    Lin, Kuang-I.; Chen, Yen-Jen; Wang, Bo-Yan; Cheng, Yung-Chen; Chen, Chang-Hsiao

    2016-03-01

    Room-temperature photoreflectance (PR) and reflectance (R) spectroscopy are utilized to investigate the near-band-edge transitions of molybdenum disulfide (MoS2) thin films grown on sapphire substrates by a hot-wall chemical vapor deposition system. The layer thickness and optical properties of the MoS2 thin films are confirmed by Raman spectroscopy, atomic force microscope, and photoluminescence (PL) analysis. The B exciton shows relatively weak PL intensity in comparing with the A exciton even for monolayer MoS2 films. In the R spectrum of few-layer MoS2, it is not possible to clearly observe exciton related features. The PR spectra have two sharp, derivative-like features on a featureless background. Throughout the PR lineshape fitting, the transition energies are designated as the A and B excitons at the K-point of the Brillouin zone, but at room temperature there seems to be no distinguishable feature corresponding to an H-point transition for the mono- and few-layer MoS2 films unlike in bulk. These transition energies are slightly larger than those obtained by PL, which is attributed to the Stokes shifts related to doping level. The obtained values of valence-band spin-orbit splitting are in good agreement with those from other experimental methods. By comparing the PR lineshapes, the dominant modulation mechanism is attributed to variations of the exciton transition energies due to change in the built-in electric field. On the strength of this study, PR spectroscopy is demonstrated as a powerful technique for characterizing the near-band-edge transitions of MoS2 from monolayer to bulk.

  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. PMID:23934494

  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. Towards atomic resolution in sodium titanate nanotubes using near-edge X-ray-absorption fine-structure spectromicroscopy combined with multichannel multiple-scattering calculations

    PubMed Central

    Krüger, Peter; Lagos, Maureen J; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris; Umek, Polona; Guttmann, Peter

    2012-01-01

    Summary Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS–TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 104 and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS–TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice. These can even be distinguished from the contribution of different hydroxyl groups to the electronic structure of the (Na,H)TiNTs. PMID:23213642

  14. Towards atomic resolution in sodium titanate nanotubes using near-edge X-ray-absorption fine-structure spectromicroscopy combined with multichannel multiple-scattering calculations.

    PubMed

    Bittencourt, Carla; Krüger, Peter; Lagos, Maureen J; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Ewels, Chris; Umek, Polona; Guttmann, Peter

    2012-01-01

    Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS-TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 10(4) and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS-TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice. These can even be distinguished from the contribution of different hydroxyl groups to the electronic structure of the (Na,H)TiNTs. PMID:23213642

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

    PubMed

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

    2013-05-28

    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

  16. 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

  17. Ge L{sub 3}-edge x-ray absorption near-edge structure study of structural changes accompanying conductivity drift in the amorphous phase of Ge{sub 2}Sb{sub 2}Te{sub 5}

    SciTech Connect

    Mitrofanov, K. V.; Kolobov, A. V. Fons, P.; Wang, X.; Tominaga, J.; Tamenori, Y.; Uruga, T.; Ciocchini, N.; Ielmini, D.

    2014-05-07

    A gradual uncontrollable increase in the resistivity of the amorphous phase of phase-change alloys, such as Ge{sub 2}Sb{sub 2}Te{sub 5}, known as drift, is a serious technological issue for application of phase-change memory. While it has been proposed that drift is related to structural relaxation, no direct structural results have been reported so far. Here, we report the results of Ge L{sub 3}-edge x-ray absorption measurements that suggest that the drift in electrical conductivity is associated with the gradual conversion of tetrahedrally coordinated Ge sites into pyramidal sites, while the system still remains in the amorphous phase. Based on electronic configuration arguments, we propose that during this process, which is governed by the existence of lone-pair electrons, the concentration of free carriers in the system decreases resulting in an increase in resistance despite the structural relaxation towards the crystalline phase.

  18. 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.

  19. Collision-Induced Absorption by H2 Pairs in the Second Overtone Band at 298 and 77.5 K: Comparison between Experimental and Theoretical Results

    NASA Technical Reports Server (NTRS)

    Brodbeck, C.; Bouanich, J.-P.; van-Thanh, Nguyen; Fu, Y.; Borysow, A.

    1999-01-01

    The collision-induced spectra of hydrogen in the region of the second overtone at 0.8 microns have been recorded at temperatures of 298 and 77.5 K and for gas densities ranging from 100 to 800 amagats. The spectral profile defined by the absorption coefficient per squared density varies significantly with the density, so that the binary absorption coefficient has been determined by extrapolations to zero density of the measured profiles. Our extrapolated measurements and our recent ab initio quantum calculation are in relatively good agreement with one another. Taking into account the very weak absorption of the second overtone band, the agreement is, however, not as good as it has become (our) standard for strong bands.

  20. Estimation of variability of specific absorption rate with physical description of children exposed to electromagnetic field in the VHF band.

    PubMed

    Nagaoka, T; Watanabe, S

    2009-01-01

    Recently, there has been an increasing concern regarding the effects of electromagnetic waves on the health of humans. The safety of radio frequency electromagnetic fields (RF-EMFs) is evaluated by the specific absorption rate (SAR). In recent years, SAR has been estimated by numerical simulation using fine-resolution and anatomically realistic reference whole-body voxel models of people of various ages. The variation in SAR with a change in the physical features of a real person is hardly studied, although every person has different physical features. In this study, in order to estimate the individual variability in SAR of persons, we obtained considerable 3D body shape data from actual three-year-old children and developed several homogeneous models of these children. The variability in SAR of the homogeneous models of three-year-old children for whole-body exposure to RF electromagnetic fields in the very high frequency (VHF) band calculated using the finite-difference time-domain method has been described. PMID:19964253

  1. Microwave-assisted synthesis of graphene-Ni composites with enhanced microwave absorption properties in Ku-band

    NASA Astrophysics Data System (ADS)

    Zhu, Zetao; Sun, Xin; Li, Guoxian; Xue, Hairong; Guo, Hu; Fan, Xiaoli; Pan, Xuchen; He, Jianping

    2015-03-01

    Recently, graphene has been applied as a new microwave absorber because of its high dielectric loss and low density. Nevertheless, the high dielectric constant of pristine graphene has caused unbalanced electromagnetic parameters and results in a bad impedance matching characteristic. In this study, we report a facile microwave-assisted heating approach to produce reduced graphene oxide-nickel (RGO-Ni) composites. The phase and morphology of as-synthesized RGO-Ni composites are characterized by XRD, Raman, FESEM and TEM. The results show that Ni nanoparticles with a diameter around 20 nm are grown densely and uniformly on the RGO sheets. In addition, enhanced microwave absorption properties in Ku-band of RGO-Ni composites is mainly due to the synergistic effect of dielectric loss and magnetic loss and the dramatically electron polarizations caused by the formation of large conductive network. The minimum reflection loss of RGO-Ni-2 composite with the thickness of 2 mm can reaches -42 dB at 17.6 GHz. The RGO-Ni composite is an attractive candidate for the new type of high performance microwave absorbing material.

  2. 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

    2016-04-01

    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. PMID:26959687

  3. High resolution absorption cross sections in the transmission window region of the Schumann-Runge bands and Herzberg continuum of O2

    NASA Technical Reports Server (NTRS)

    Yoshino, K.; Esmond, J. R.; Cheung, A. S.-C.; Freeman, D. E.; Parkinson, W. H.

    1992-01-01

    Results are presented on measurements, conducted in the wavelength region 180-195 nm, and at different pressures of oxygen (between 2.5-760 torr) in order to separate the pressure-dependent absorption from the main cross sections, of the absorption cross sections of the Schumann-Runge bands in the window region between the rotational lines of S-R bands of O2. The present cross sections supersede the earlier published cross sections (Yoshino et al., 1983). The combined cross sections are presented graphically; they are available at wavenumber intervals of about 0.1/cm from the National Space Science Data Center. The Herzberg continuum cross sections are derived after subtracting calculated contributions from the Schumann-Runge bands. These are significantly smaller than any previous measurements.

  4. 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.

  5. The Protonation States of Oxo-Bridged MnIV-Dimers Resolved by Experimental and Computational Mn K Pre-Edge X-Ray Absorption Spectroscopy

    PubMed Central

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

    2013-01-01

    In nature, the protonation of oxo bridges is a commonly encountered mechanism for fine-tuning chemical properties and reaction pathways. Often, however, the protonation states are difficult to establish experimentally. This is of particular importance in the oxygen evolving complex of Photosystem II, where identification of the bridging oxo protonation states is one of the essential requirements toward unraveling the mechanism. In order to establish a combined experimental and theoretical protocol for the determination of protonation states, we have systematically investigated a series of Mn model complexes by Mn K pre-edge X-ray absorption spectroscopy. An ideal test case for selective bis-μ-oxo-bridge protonation in a Mn-dimer is represented by the system [MnIV2(salpn)2(μ-OH(n))2](n+). Although the three species [MnIV2(salpn)2(μ-O)2], [MnIV2(salpn)2(μ-O)(μ-OH)]+ and [MnIV2(salpn)2(μ-OH)2]2+ differ only in the protonation of the oxo bridges, they exhibit distinct differences in the pre-edge region while maintaining the same edge energy. The experimental spectra are correlated in detail to theoretical ly calculated spectra. A time-dependent density functional theory approach for calculating the pre-edge spectra of molecules with multiple metal centers is presented, using both high-spin (HS) and broken-symmetry (BS) electronic structure solutions. The most intense pre-edge transitions correspond to an excitation of the Mn-1s core electrons into the unoccupied orbitals of local eg character (dz2 and dxy based in the chosen coordinate system). The lowest by energy experimental feature is dominated by excitations of 1s-α electrons and the second observed feature is primarily attributed to 1s-β electron excitations. The observed energetic separation is due to spin polarization effects in spin-unrestricted density functional theory and models final state multiplet effects. The effects of spin polarization on the calculated Mn K pre-edge spectra, in both the HS

  6. Electronic structure and optic absorption of phosphorene under strain

    NASA Astrophysics Data System (ADS)

    Duan, Houjian; Yang, Mou; Wang, Ruiqiang

    2016-07-01

    We studied the electronic structure and optic absorption of phosphorene (monolayer of black phosphorus) under strain. Strain was found to be a powerful tool for the band structure engineering. The in-plane strain in armchair or zigzag direction changes the effective mass components along both directions, while the vertical strain only has significant effect on the effective mass in the armchair direction. The band gap is narrowed by compressive in-plane strain and tensile vertical strain. Under certain strain configurations, the gap is closed and the energy band evolves to the semi-Dirac type: the dispersion is linear in the armchair direction and is gapless quadratic in the zigzag direction. The band-edge optic absorption is completely polarized along the armchair direction, and the polarization rate is reduced when the photon energy increases. Strain not only changes the absorption edge (the smallest photon energy for electron transition), but also the absorption polarization.

  7. Effect of a Coadsorbent on the Performance of Dye-Sensitized TiO2 Solar Cells: Shielding versus Band-Edge Movement

    SciTech Connect

    Frank, A. J.; Neale, N. R.; Kopidakis, N.; van de Lagemaat, J.; Gratzel, M.

    2005-11-01

    The objective of this research is to determine the operational characteristics key to efficient, low-cost, stable solar cells based on dye-sensitized mesoporous films (in collaboration with DOE's Office of Science Program). Toward this end, we have investigated the mechanism by which the adsorbent chenodeoxycholate, cografted with a sensitizer onto TiO2 nanocrystals, improves the open-circuit photovoltage (VOC) and short-circuit photocurrent density (JSC). We find that adding chenodeoxycholate not only shifts the TiO2 conduction-band edge to negative potentials but also accelerates the rate of recombination. The net effect of these opposing phenomena is to produce a higher photovoltage. It is also found that chenodeoxycholate reduces the dye loading significantly but has only a modest effect on JSC. Implications of these results to developing more efficient cells are discussed.

  8. Band-edge optical transitions in a nonpolar-plane GaN substrate: exciton–phonon coupling and temperature effects

    NASA Astrophysics Data System (ADS)

    Wang, M. Z.; Xu, S. J.

    2016-09-01

    We present a detailed investigation of the band-edge optical transitions involving the interacting exciton–phonon system, especially first-order longitudinal optical (LO) phonon-assisted luminescence of bound and free excitons in m- and c-plane GaN substrates in a low temperature range from 4 K to 40 K. The main luminescence features of all of the three kinds of excitons can be well described by the theoretical models that take exciton-LO-phonon coupling into account. The effective Bohr radii of the excitons play a key role in determining the Huang–Rhys factor characterizing the exciton-LO-phonon coupling strength in GaN. An interesting oscillatory structure is found to appear in the low-temperature luminescence spectra of the nonpolar-plane GaN substrate, which needs to be clarified by further investigations.

  9. Energy distribution measurement of narrow-band ultrashort x-ray beams via K-edge filters subtraction

    SciTech Connect

    Cardarelli, Paolo; Di Domenico, Giovanni; Marziani, Michele; Mucollari, Irena; Pupillo, Gaia; Sisini, Francesco; Taibi, Angelo; Gambaccini, Mauro

    2012-10-01

    The characterization of novel x-ray sources includes the measurement of the photon flux and the energy distribution of the produced beam. The aim of BEATS2 experiment at the SPARC-LAB facility of the INFN National Laboratories of Frascati (Rome, Italy) is to investigate possible medical applications of an x-ray source based on Thomson relativistic back-scattering. This source is expected to produce a pulsed quasi-monochromatic x-ray beam with an instantaneous flux of 10{sup 20} ph/s in pulses 10 ps long and with an average energy of about 20 keV. A direct measurement of energy distribution of this beam is very difficult with traditional detectors because of the extremely high photon flux. In this paper, we present a method for the evaluation of the energy distribution of quasi-monochromatic x-ray beams based on beam filtration with K-edge absorbing foils in the energy range of interest (16-22 keV). The technique was tested measuring the energy distribution of an x-ray beam having a spectrum similar to the expected one (SPARC-LAB Thomson source) by using a tungsten anode x-ray tube properly filtered and powered. The energy distribution obtained has been compared with the one measured with a HPGe detector showing very good agreement.

  10. Surface passivation of a photonic crystal band-edge laser by atomic layer deposition of SiO2 and its application for biosensing.

    PubMed

    Cha, Hyungrae; Lee, Jeongkug; Jordan, Luke R; Lee, Si Hoon; Oh, Sang-Hyun; Kim, Hyo Jin; Park, Juhun; Hong, Seunghun; Jeon, Heonsu

    2015-02-28

    We report on the conformal surface passivation of photonic crystal (PC) laser devices with an ultrathin dielectric layer. Air-bridge-type Γ-point band-edge lasers (BELs) are fabricated by forming a honeycomb lattice two-dimensional PC structure into an InGaAsP multiple-quantum-well epilayer. Atomic layer deposition (ALD) is employed for conformal deposition of a few-nanometer-thick SiO2 layer over the entire device surface, not only on the top and bottom surfaces of the air-bridge membrane but also on the air-hole sidewalls. Despite its extreme thinness, the ALD passivation layer is found to protect the InGaAsP BEL devices from harsh chemicals. In addition, the ALD-SiO2 is compatible with the silane-based surface chemistry, which allows us to use ALD-passivated BEL devices as label-free biosensors. The standard streptavidin-biotin interaction shifts the BEL lasing wavelength by ∼1 nm for the dipole-like Γ-point band-edge mode. A sharp lasing line (<0.2 nm, full width at half-maximum) and a large refractive index sensitivity (∼163 nm per RIU) produce a figure of merit as high as ∼800 for our BEL biosensor, which is at least an order of magnitude higher than those of more common biosensors that rely on a broad resonance peak, showing that our nanolaser structures are suitable for highly sensitive biosensor applications. PMID:25631610

  11. Analysis of Mars surface hydration through the MEx/OMEGA observation of the 3 μm absorption band.

    NASA Astrophysics Data System (ADS)

    Jouglet, D.; Poulet, F.; Bibring, J. P.; Langevin, Y.; Gondet, B.; Milliken, R. E.; Mustard, J. F.

    The near infrared Mars surface global mapping done by OMEGA gives the first opportunity to study the global and detailed characteristics of the 3µm hydration absorption band on Mars surface. This feature is indistinctly due to bending and stretching vibrations of water bound in minerals or adsorbed at their surface, and of hydroxyl groups (for a review, see e.g. [1] or [2]). Its study may give new elements to determine the geologic and climatic past of Mars, and may put new constrain about the current water cycle of Mars. OMEGA data are processed in a pipeline that converts raw data to radiance, removes atmospheric effects and gets I/F. Specific data reduction scheme has been developed to assess temperature of OMEGA spectra at 5 µm and to remove their thermal part so as to get the albedo from 1.µm to 5.1µm ([2]). Two methods, the Integrated Band Depth and the water content based on comparison with laboratory measures of Yen et al. ([3]), have been used to assess the 3µm band depth. These two methods where applied to OMEGA spectra acquired at a nominal calibration level and not exhibiting water ice features. This corresponds to approximately 35 million spectra ([2]). The data processed show the presence of this absorption feature overall the Martian surface, which could be explained by the presence of adsorbed water up to 1% water mass percentage ([4]) and by rinds or coating resulting from weathering (see e.g. [5] or [6]). A possible increase of hydration with albedo is discussed so as to discriminate between the albedo-dependence of the method and hydration variations. Terrains enriched in phyllosilicates ([7]), sulfates ([8]) or hydroxides exhibit an increased hydration at 3 µm. This terrains show that the 3 µm band can bring additional information about composition, for example by observing a variation in the shape of the band. A decrease of hydration with elevation is observed on the processed data independently of the value of albedo. This correlation

  12. On the importance of nuclear quantum motions in near edge x-ray absorption fine structure (NEXAFS) spectroscopy of molecules

    SciTech Connect

    Schwartz, Craig P.; Uejio, Janel S.; Saykally, Richard J.; Prendergast, David

    2009-02-26

    We report the effects of sampling nuclear quantum motion with path integral molecular dynamics (PIMD) on calculations of the nitrogen K-edge spectra of two isolated organic molecules. S-triazine, a prototypical aromatic molecule occupying primarily its vibrational ground state at room temperature, exhibits substantially improved spectral agreement when nuclear quantum effects are included via PIMD, as compared to the spectra obtained from either a single fixed-nuclei based calculation or from a series of configurations extracted from a classical molecular dynamics trajectory. Nuclear quantum dynamics can accurately explain the intrinsic broadening of certain features. Glycine, the simplest amino acid, is problematic due to large spectral variations associated with multiple energetically accessible conformations at the experimental temperature. This work highlights the sensitivity of NEXAFS to quantum nuclear motions in molecules, and the necessity of accurately sampling such quantum motion when simulating their NEXAFS spectra.

  13. Study of hard disk and slider surfaces using X-ray photoemission electron microscopy and near-edge X-ray absorption fine structure spectroscopy

    SciTech Connect

    Anders, S.; Stammler, T.; Bhatia, C.S.; Fong, W.; Chen, C.Y.; Bogy, D.B.

    1998-04-01

    X-ray Photo Emission Electron Microscopy (X-PEEM) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy were applied to study the properties of amorphous hard carbon overcoats on disks and sliders, and the properties of the lubricant. The modification of lubricants after performing thermal desorption studies was measured by NEXAFS, and the results are compared to the thermal desorption data. The study of lubricant degradation in wear tracks is described. Sliders were investigated before and after wear test, and the modification of the slider coating as well as the transfer of lubricant to the slider was studied. The studies show that the lubricant is altered chemically during the wear. Fluorine is removed and carboxyl groups are formed.

  14. Liquid crystal alignment on ion-beam-treated polyimide with a long alkyl side chain: near edge X-ray absorption fine structure spectroscopy analysis.

    PubMed

    Seo, Joo-Hong; Hwang, Soo Won; Song, Dong Han; Shin, Jae Hoon; Yoon, Tae-Hoon; Kim, Jae Chang; Yi, Mi Hye

    2009-02-19

    Liquid crystal alignment on ion-beam-treated polyimides with a long alkyl side chain was investigated using near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The long alkyl side chains and the asymmetric distribution and orientational order of the pi-bonds of the polyimide surface can be determined by analyzing the angular dependent resonance intensities of the NEXAFS measurements. Herein, we demonstrate that the pretilt angle of the LC cell made by our method decreases as more long alkyl side chains are destroyed. Additionally, the tilt direction of the LC molecules can be determined from the asymmetric distribution of pi-bonds of the polyimide created by the ion beam irradiation. PMID:19161281

  15. Particle Formation from Pulsed Laser Irradiation of SootAggregates studied with scanning mobility particle sizer, transmissionelectron microscope and near-edge x-ray absorption fine structure.

    SciTech Connect

    Michelsen, Hope A.; Tivanski, Alexei V.; Gilles, Mary K.; vanPoppel, Laura H.; Dansson, Mark A.; Buseck, Peter R.; Buseck, Peter R.

    2007-02-20

    We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes.

  16. Near edge X-ray absorption fine structure spectroscopy as a tool to probe electronic and structural properties of thin organic films and liquids.

    PubMed

    Hähner, Georg

    2006-12-01

    Synchrotron-based spectroscopic techniques have contributed significantly to a better understanding of the properties of materials on the macroscopic and microscopic scale over the last decades. They can be applied to samples from a diversity of fields, including Biology, Life Sciences, Chemistry and Materials. One of these techniques is Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, revealing electronic structure and information on the orientation of adsorbed molecules. The present article describes the basics of the technique and the progress it has made over the last three decades, and summarizes some of its more recent developments and applications. This tutorial review article should be accessible for novices to the field from Physics, Chemistry, Biology, Materials, and the Life Sciences, interested in thin organic films and liquid systems. PMID:17225886

  17. Investigation of Pb species in soils, celery and duckweed by synchrotron radiation X-ray absorption near-edge structure spectrometry

    NASA Astrophysics Data System (ADS)

    Luo, Liqiang; Shen, Yating; Liu, Jian; Zeng, Yuan

    2016-08-01

    The Pb species play a key role in its translocation in biogeochemical cycles. Soils, sediments and plants were collected from farmlands around Pb mines, and the Pb species in them was identified by X-ray absorption near-edge structure spectrometry. In soils, Pb5(PO4)3Cl and Pb3(PO4)2 were detected, and in sediments, Pb-fulvic acids (FAs) complex was identified. A Pb complex with FA fragments was also detected in celery samples. We found that (1) different Pb species were present in soils and sediments; (2) the Pb species in celery, which was grown in sediments, was different from the species present in duckweed, which grew in water; and (3) a Pb-FA-like compound was present in celery roots. The newly identified Pb species, the Pb-FA-like compound, may play a key role in Pb tolerance and translocation within plants.

  18. X-ray absorption spectra of nucleotides (AMP, GMP, and CMP) in liquid water solutions near the nitrogen K-edge

    NASA Astrophysics Data System (ADS)

    Ukai, Masatoshi; Yokoya, Akinari; Fujii, Kentaro; Saitoh, Yuji

    2010-07-01

    The X-ray absorption of nucleotides (adenosine-5'-monophosphate, guanosine 5'-monophosphate, and cytidine 5'-monophosphate) are measured in both water solutions and thin solid films at X-ray energies near the nitrogen K-edge in the 'water-window' region. Each spectrum corresponds to the selective excitation of a nucleobase site in a nucleotide, and thus has features similar to the spectrum of the corresponding nucleobase. An additional new peak in the energy region of the nitrogen 1s → π* resonance is observed for each nucleotide. No significant difference between the water solutions and thin solid films is found, which might be attributable to the hydrophobic properties of a nucleobase in a nucleotide.

  19. Composition analysis of a polymer electrolyte membrane fuel cell microporous layer using scanning transmission X-ray microscopy and near edge X-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    George, Michael G.; Wang, Jian; Banerjee, Rupak; Bazylak, Aimy

    2016-03-01

    The novel application of scanning transmission X-ray microscopy (STXM) to the microporous layer (MPL) of a polymer electrolyte membrane fuel cell is investigated. A spatially resolved chemical component distribution map is obtained for the MPL of a commercially available SGL 25 BC sample. This is achieved with near edge X-ray absorption fine structure spectroscopic analysis. Prior to analysis the sample is embedded in non-reactive epoxy and ultra-microtomed to a thickness of 100 nm. Polytetrafluoroethylene (PTFE), carbon particle agglomerates, and supporting epoxy resin distributions are identified and reconstructed for a scanning area of 6 μm × 6 μm. It is observed that the spatial distribution of PTFE is strongly correlated to the carbon particle agglomerations. Additionally, agglomerate structures of PTFE are identified, possibly indicating the presence of a unique mesostructure in the MPL. STXM analysis is presented as a useful technique for the investigation of chemical species distributions in the MPL.

  20. Effect of gas residence time on near-edge X-ray absorption fine structures of hydrogenated amorphous carbon films grown by plasma-enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Jia, Lingyun; Sugiura, Hirotsugu; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Oda, Osamu; Sekine, Makoto; Hiramatsu, Mineo; Hori, Masaru

    2016-04-01

    In hydrogenated amorphous carbon films, deposited using a radical-injection plasma-enhanced chemical vapor deposition system, the chemical bonding structure was analyzed by near-edge X-ray absorption fine-structure spectroscopy. With a change in the residence times of source gases in a reactor, whereby total gas flow rates of H2/CH4 increased from 50 to 400 sccm, sp2-C fractions showed the minimum value at 150 sccm, while H concentration negligibly changed according to the results of secondary ion mass spectroscopy. On the other hand, widths of σ* C-C peaks increased with decreasing gas residence time, which indicates an increase in the fluctuation of bonding structures.

  1. Radiative analysis of global mean temperature trends in the middle atmosphere: Effects of non-locality and secondary absorption bands

    NASA Astrophysics Data System (ADS)

    Fomichev, V. I.; Jonsson, A. I.; Ward, W. E.

    2016-02-01

    In this paper, we provide a refined and extended assignment of past and future temperature changes relative to previous analyses and describe and evaluate the relevance of vertical coupling and non-linear and secondary radiative mechanisms for the interpretation of climatic temperature variations in the middle atmosphere. Because of their nature, the latter mechanisms are not adequately accounted for in most regression analyses of temperature trends as a function of local constituent variations. These mechanisms are examined using (1) globally averaged profiles from transient simulations with the Canadian Middle Atmosphere Model (CMAM) forced by changes in greenhouse gases and ozone depleting substances and (2) a one-dimensional radiative-equilibrium model forced using the diagnosed global mean changes in radiatively active constituents as derived from the CMAM model runs. The conditions during the periods 1975 to 1995 and 2010 to 2040 (during which the rates of change in ozone and CO2 differ) provide a suitable contrast for the role of the non-linear and non-local mechanisms being evaluated in this paper to be clearly differentiated and evaluated. Vertical coupling of radiative transfer effects and the influence of secondary absorption bands are important enough to render the results of multiple linear regression analyses between the temperature response and constituent changes misleading. These effects are evaluated in detail using the 1D radiative-equilibrium model using profiles from the CMAM runs as inputs. In order to explain the differences in the CMAM temperature trends prior to and after 2000 these other radiative effects must be considered in addition to local changes in the radiatively active species. The middle atmosphere temperature cools in response to CO2 and water vapor increases, but past and future trends are modulated by ozone changes.

  2. Near-band-edge photoluminescence emission in Al{sub x}Ga{sub 1{minus}x}N under high pressure

    SciTech Connect

    Shan, W.; Ager, J.W. III; Walukiewicz, W.; Haller, E.E.; Little, B.D.; Song, J.J.; Schurman, M.; Feng, Z.C.; Stall, R.A.; Goldenberg, B.

    1998-05-01

    We present results of pressure-dependent photoluminescence (PL) studies of single-crystal Al{sub x}Ga{sub 1{minus}x}N epitaxial films grown on sapphire substrates by metalorganic chemical vapor deposition. PL measurements were performed under hydrostatic pressure using the diamond-anvil-cell technique. PL spectra taken from the Al{sub x}Ga{sub 1{minus}x}N epitaxial films are dominated by strong near-band-edge luminescence emissions. The emission lines were found to shift linearly towards higher energy with increasing pressure. By examining the pressure dependence of the spectral features, the pressure coefficients for the PL emissions associated with the direct {Gamma} band gap of Al{sub x}Ga{sub 1{minus}x}N were determined. Our results yield a pressure coefficient of 4.0{times}10{sup {minus}3}eV/kbar for Al{sub 0.05}Ga{sub 0.95}N and 3.6{times}10{sup {minus}3}eV/kbar for Al{sub 0.35}Ga{sub 0.65}N. {copyright} {ital 1998 American Institute of Physics.}

  3. Observation of near-band-edge photoluminescence and UV photoresponse in near-stoichiometric Zn2SnO4 nanowires

    NASA Astrophysics Data System (ADS)

    Tien, Li-Chia; Yang, Shang-Jan; Chen, Ya-Han; Ho, Ching-Hwa

    2016-06-01

    Single-phase, near-stoichiometric zinc stannate (Zn2SnO4) nanowires were synthesized by a direct vapor transport process on c-Al2O3 substrates under optimized growth conditions. The optimal growth temperature for Zn2SnO4 nanowires is above 700 °C. Structural characterization indicates that the nanowires had the single crystal cubic spinel structure and diameters of ∼90 nm and they grew in the [1\\bar{1}\\bar{1}] direction. Low-temperature photoluminescence (PL) shows a strong emission peak at 3.7 eV, attributed to the near-band-edge-emission of Zn2SnO4 nanowires. Temperature-dependent PL results are consistent with the Varshni equation, and the band gap is redshifted by ∼170 meV as the temperature is increased from 11 to 300 K. The obtained direct gap of Zn2SnO4 nanowires is 3.546 eV at 300 K. A UV photodetector based on as-grown Zn2SnO4 nanowires was fabricated by a simple and cost-effective process. The Zn2SnO4 nanowires exhibited UV photoconductivity, and good selectivity and decent response to UV. The efficient fabrication method, high chemical and thermal stability of the Zn2SnO4 nanowire UV photodetector made it very suitable for use in harsh environments.

  4. Attainment of dual-band edge work function by using a single metal gate and single high-k dielectric via ion implantation for HP CMOS device

    NASA Astrophysics Data System (ADS)

    Xu, Qiuxia; Xu, G.; Zhou, H.; Zhu, H.; Liu, J.; Wang, Y.; Li, J.; Xiang, J.; Liang, Q.; Wu, H.; Zhong, J.; Xu, M.; Xu, W.; Ma, X.; Wang, X.; Tong, X.; Chen, D.; Yan, J.; Zhao, C.; Ye, T.

    2016-01-01

    Attainment of dual band-edge effective work functions by using a single metal gate and single high k gate dielectric via P/BF2 implantation into a TiN metal gate for HP HKMG CMOS device applications are investigated under a gate-last process flow for the first time. The flat band voltage (VFB) modulations of about -750 mV/570 mV for N-/P-type MOS device with P/BF2 implanted TiN/HfO2/ILSiO2 gate stack are obtained respectively in the experiment range. Suitable low threshold voltages of CMOSFETs are gotten while simultaneously shrinking the EOT. The effects of P/BF2 ion implantation energy, dose and TiN gate thickness on the properties of implanted TiN/HfO2/ILSiO2 gate stack are studied, the possible mechanisms are discussed. This technique has been successfully integrated into the fabrications of aggressively scaled HP HKMG CMOSFETs and 32 CMOS frequency dividers under a gate-last process flow.

  5. Uncovering the mechanism for selective control of the visible and near-IR absorption bands in bacteriochlorophylls a, b and g

    PubMed Central

    Fujisawa, Jun-ichi; Nagata, Morio

    2014-01-01

    Bacteriochlorophylls (BChls) play an important role as light harvesters in photosynthetic bacteria. Interestingly, bacteriochlorophylls (BChls) a, b, and g selectively tune their visible (Qx) and near IR (Qy) absorption bands by the substituent changes. In this paper, we theoretically study the mechanism for the selective control of the absorption bands. Density functional theory (DFT) and time-dependent DFT (TD-DFT) and four-orbital model analyses reveal that the selective red-shift of the Qy band with the substituent change from BChl a to b occurs with the lower-energy shift of the (HOMO, LUMO) excited state directly induced by the molecular-orbital energy changes. In contrast, the Qx band hardly shifts by the cancellation between the higher- and lower-energy shifts of the (HOMO-1, LUMO) excited state directly induced by the molecular-orbital energy changes and configuration interaction, respectively. On the other hand, with the substituent changes from BChl a to g, the Qx band selectively blue-shifts by the larger higher-energy shift of the (HOMO-1, LUMO) excited state directly induced by the molecular-orbital energy shifts than the lower-energy shift due to the configuration interaction. In contrast, the Qy band hardly shifts by the cancellation between the higher- and lower-energy shifts of the (HOMO, LUMO) excited state directly induced by the molecular-orbital energy changes and configuration interaction, respectively. Our work provides the important knowledge for understanding how nature controls the light-absorption properties of the BChl dyes, which might be also useful for design of porphyrinoid chromophores. PMID:27493495

  6. Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis

    PubMed Central

    Meirer, Florian; Pemmer, Bernhard; Pepponi, Giancarlo; Zoeger, Norbert; Wobrauschek, Peter; Sprio, Simone; Tampieri, Anna; Goettlicher, Joerg; Steininger, Ralph; Mangold, Stefan; Roschger, Paul; Berzlanovich, Andrea; Hofstaetter, Jochen G.; Streli, Christina

    2011-01-01

    A highly specific accumulation of the toxic element lead was recently measured in the transition zone between non-calcified and calcified normal human articular cartilage. This transition zone, the so-called ‘tidemark’, is considered to be an active calcification front of great clinical importance. However, little is known about the mechanisms of accumulation and the chemical form of Pb in calcified cartilage and bone. Using spatially resolved X-ray absorption near-edge structure analysis (µ-XANES) at the Pb L 3-edge, the chemical state of Pb in the osteochondral region was investigated. The feasibility of the µ-XANES set-up at the SUL-X beamline (ANKA synchrotron light source) was tested and confirmed by comparing XANES spectra of bulk Pb-reference compounds recorded at both the XAS and the SUL-X beamline at ANKA. The µ-XANES set-up was then used to investigate the tidemark region of human bone (two patella samples and one femoral head sample). The spectra recorded at the tidemark and at the trabecular bone were found to be highly correlated with the spectra of synthetic Pb-doped carbonated hydroxyapatite, suggesting that in both of these very different tissues Pb is incorporated into the hydroxyapatite structure. PMID:21335911

  7. Three-dimensional Fe speciation of an inclusion cloud within an ultradeep diamond by confocal μ-X-ray absorption near edge structure: evidence for late stage overprint.

    PubMed

    Silversmit, Geert; Vekemans, Bart; Appel, Karen; Schmitz, Sylvia; Schoonjans, Tom; Brenker, Frank E; Kaminsky, Felix; Vincze, Laszlo

    2011-08-15

    A stream of 1-20 μm sized mineral inclusions having the negative crystal shape of its host within an "ultra-deep" diamond from Rio Soriso (Juina area, Mato Grosso State, Brazil) has been studied with confocal μ-X-ray absorption near edge structure (μXANES) at the Fe K and Mn K edges. This technique allows the three-dimensional nondestructive speciation of the Fe and Mn containing minerals within the inclusion cloud. The observed Fe-rich inclusions were identified to be ferropericlase (Fe,Mg)O, hematite and a mixture of these two minerals. Confocal μ-X-ray fluorescence (μXRF) further showed that Ca-rich inclusions were present as well, which are spatially separated from or in close contact with the Fe-rich inclusions. The inclusions are aligned along a plane, which most likely represents a primary growth zone. In the close vicinity of the inclusions, carbon coated planar features are visible. The three-dimensional distribution indicates a likely fluid overprint along an open crack. Our results imply that an imposed negative diamond shape of an inclusion alone does not exclude epigenetic formation or intense late stage overprint. PMID:21707095

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

    PubMed

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

    2016-01-12

    Orthogonality constrained density functional theory (OCDFT) provides near-edge X-ray absorption (NEXAS) spectra of first-row elements within one electronvolt from experimental values. However, with increasing atomic number, scalar relativistic effects become the dominant source of error in a nonrelativistic OCDFT treatment of core-valence excitations. In this work we report a novel implementation of the spin-free exact-two-component (X2C) one-electron treatment of scalar relativistic effects and its combination with a recently developed OCDFT approach to compute a manifold of core-valence excited states. The inclusion of scalar relativistic effects in OCDFT reduces the mean absolute error of second-row elements core-valence excitations from 10.3 to 2.3 eV. For all the excitations considered, the results from X2C calculations are also found to be in excellent agreement with those from low-order spin-free Douglas-Kroll-Hess relativistic Hamiltonians. The X2C-OCDFT NEXAS spectra of three organotitanium complexes (TiCl4, TiCpCl3, TiCp2Cl2) are in very good agreement with unshifted experimental results and show a maximum absolute error of 5-6 eV. In addition, a decomposition of the total transition dipole moment into partial atomic contributions is proposed and applied to analyze the nature of the Ti pre-edge transitions in the three organotitanium complexes. PMID:26584082

  9. Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy.

    PubMed

    Altman, Alison B; Pacold, Joseph I; Wang, Jian; Lukens, Wayne W; Minasian, Stefan G

    2016-06-14

    The electronic structure in the complete series of stable lanthanide sesquioxides, Ln2O3 (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy (XAS) with a scanning transmission X-ray microscope (STXM). The experimental results agree with recent synthetic, spectroscopic and theoretical investigations that provided evidence for 5d orbital involvement in lanthanide bonding, while confirming the traditional viewpoint that there is little Ln 4f and O 2p orbital mixing. However, the results also showed that changes in the energy and occupancy of the 4f orbitals can impact Ln 5d and O 2p mixing, leading to several different bonding modes for seemingly identical Ln2O3 structures. On moving from left to right in the periodic table, abrupt changes were observed for the energy and intensity of transitions associated with Ln 5d and O 2p antibonding states. These changes in peak intensity, which were directly related to the amounts of O 2p and Ln 5d mixing, were closely correlated to the well-established trends in the chemical accessibility of the 4f orbitals towards oxidation or reduction. The unique insight provided by the O K-edge XAS is discussed in the context of several recent theoretical and physical studies on trivalent lanthanide compounds. PMID:26979662

  10. X-ray absorption near-edge structure and nuclear magnetic resonance study of the lithium-sulfur battery and its components.

    PubMed

    Patel, Manu U M; Arčon, Iztok; Aquilanti, Giuliana; Stievano, Lorenzo; Mali, Gregor; Dominko, Robert

    2014-04-01

    Understanding the mechanism(s) of polysulfide formation and knowledge about the interactions of sulfur and polysulfides with a host matrix and electrolyte are essential for the development of long-cycle-life lithium-sulfur (Li-S) batteries. To achieve this goal, new analytical tools need to be developed. Herein, sulfur K-edge X-ray absorption near-edge structure (XANES) and (6,7) Li magic-angle spinning (MAS) NMR studies on a Li-S battery and its sulfur components are reported. The characterization of different stoichiometric mixtures of sulfur and lithium compounds (polysulfides), synthesized through a chemical route with all-sulfur-based components in the Li-S battery (sulfur and electrolyte), enables the understanding of changes in the batteries measured in postmortem mode and in operando mode. A detailed XANES analysis is performed on different battery components (cathode composite and separator). The relative amounts of each sulfur compound in the cathode and separator are determined precisely, according to the linear combination fit of the XANES spectra, by using reference compounds. Complementary information about the lithium species within the cathode are obtained by using (7) Li MAS NMR spectroscopy. The setup for the in operando XANES measurements can be viewed as a valuable analytical tool that can aid the understanding of the sulfur environment in Li-S batteries. PMID:24497200

  11. Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

    USGS Publications Warehouse

    Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael; Hill, Ronald J.; Grayson, Michael B.; Mitra-Kirtley, Sudipa; Bake, Kyle D.; Craddock, Paul R.; Abdallah, Wael; Pomerantz, Andrew E.

    2016-01-01

    The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

  12. 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

  13. Systematic Oxidation of Polystyrene by Ultraviolet-Ozone, Characterized by Near-Edge X-ray Absorption Fine Structure and Contact Angle

    SciTech Connect

    Klein,R.; Fischer, D.; Lenhart, J.

    2008-01-01

    The process of implanting oxygen in polystyrene (PS) via exposure to ultraviolet-ozone (UV-O) was systematically investigated using the characterization technique of near-edge X-ray absorption fine structure (NEXAFS). Samples of PS exposed to UV-O for 10-300 s and washed with isopropanol were analyzed using the carbon and oxygen K-edge NEXAFS partial electron yields, using various retarding bias voltages to depth-profile the oxygen penetration into the surface. Evaluation of reference polymers provided a scale to quantify the oxygen concentration implanted by UV-O treatment. We find that ozone initially reacts with the double bonds on the phenyl rings, forming carbonyl groups, but within 1 min of exposure, the ratio of double to single oxygen bonds stabilizes at a lower value. Oxygen penetrates the film with relative ease, creating a fairly uniform distribution of oxygen within at least the first 4 nm (the effective depth probed by NEXAFS here). Before oxygen accumulates in large concentrations, however, it preferentially degrades the uppermost layer of the film by removing oxygenated low-molecular-weight oligomers. The failure to accumulate high concentrations of oxygen is seen in the nearly constant carbon edge jump, the low concentration of oxygen even at 5 min exposure (58% of that in poly(4-acetoxystyrene), the polymer with the most similarities to UV-O-treated PS), and the relatively high contact angles. At 5 min exposure the oxygen concentration contains ca. 7 atomic % oxygen. The oxygen species that are implanted consist predominantly of single O-C bonds and double OC bonds but also include a small fraction of O-H. UV-O treatment leads a plateau after 2 min exposure in the water contact angle hysteresis, at a value of 67 {+-} 2, due primarily to chemical heterogeneity. Annealing above Tg allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

  14. Strong heavy-to-light hole intersubband absorption in the valence band of carbon-doped GaAs/AlAs superlattices

    NASA Astrophysics Data System (ADS)

    Hossain, M. I.; Ikonic, Z.; Watson, J.; Shao, J.; Harrison, P.; Manfra, M. J.; Malis, O.

    2013-02-01

    We report strong mid-infrared absorption of in-plane polarized light due to heavy-to-light hole intersubband transitions in the valence band of C-doped GaAs quantum wells with AlAs barriers. The transition energies are well reproduced by theoretical calculations including layer inter-diffusion. The inter-diffusion length was estimated to be 8 ± 2 Å, a value that is consistent with electron microscopy measurements. These results highlight the importance of modeling the nanoscale structure of the semiconductors for accurately reproducing intra-band transition energies of heavy carriers such as the holes.

  15. Low-temperature adsorption of H2S on Ni(001) studied by near-edge- and surface-extended-x-ray-absorption fine structure

    NASA Astrophysics Data System (ADS)

    McGrath, R.; MacDowell, A. A.; Hashizume, T.; Sette, F.; Citrin, P. H.

    1989-11-01

    The adsorption of H2S on Ni(001) has been studied with surface-extended x-ray-absorption fine structure and near-edge x-ray-absorption fine structure (NEXAFS) using the AT&T Bell Laboratories X15B beamline at the National Synchrotron Light Source. At 95 K and full saturation coverage, ~0.45 monolayer (ML) of S atoms in fourfold-hollow sites are produced, characteristic of room-temperature adsorption, accompanied by ~0.05 ML of oriented molecular H2S. Both these atomic and molecular chemisorbed species are buried under ~0.9 ML of disordered physisorbed H2S. No evidence for HS is found. Above 190 K the two molecular H2S phases desorb, leaving only dissociated S. These findings differ from previously reported interpretations of data obtained with high-resolution electron-energy-loss spectroscopy. They also exemplify the utility of NEXAFS for identifying and quantifying atomic and molecular surface species even when their difference involves only H and the two species coexist.

  16. Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K[Formula: see text] emission spectra.

    PubMed

    Rees, Julian A; Wandzilak, Aleksandra; Maganas, Dimitrios; Wurster, Nicole I C; Hugenbruch, Stefan; Kowalska, Joanna K; Pollock, Christopher J; Lima, Frederico A; Finkelstein, Kenneth D; DeBeer, Serena

    2016-09-01

    A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and K[Formula: see text] X-ray emission spectroscopies (XES). Qualitative trends within the datasets, as well as comparisons between the XAS and XES data, illustrate the information content of both methods. The complementary nature of the chemical insight highlights the success of this dual-technique approach in characterizing both the structural and electronic properties of vanadium sites. In particular, and in contrast to XAS or extended X-ray absorption fine structure (EXAFS), we demonstrate that valence-to-core XES is capable of differentiating between ligating atoms with the same identity but different bonding character. Finally, density functional theory (DFT) and time-dependent DFT calculations enable a more detailed, quantitative interpretation of the data. We also establish correction factors for the computational protocols through calibration to experiment. These hard X-ray methods can probe vanadium ions in any oxidation or spin state, and can readily be applied to sample environments ranging from solid-phase catalysts to biological samples in frozen solution. Thus, the combined XAS and XES approach, coupled with DFT calculations, provides a robust tool for the study of vanadium atoms in bioinorganic chemistry. PMID:27251139

  17. Neutralization of calcite in mineral aerosols by acidic sullur species collected in China and Japan studied by ca K-edge X-ray absorption near-edge structure.

    PubMed

    Takahashi, Yoshio; Miyoshi, Takuro; Higashi, Masayuki; Kamioka, Hikari; Kanai, Yutaka

    2009-09-01

    Calcium species in mineral aerosols collected simultaneously in Aksu (near the Taklimakan Desert), Qingdao (eastern China), and Tsukuba (Japan) during dust and nondust periods were determined using Ca K-edge X-ray absorption near-edge structure (XANES). From the fitting of XANES spectra, it was found that (i) calcite and gypsum were the main Ca species in the aerosol samples, and (ii) the gypsum fraction versus total Ca minerals [Gyp]/[Ca2+]t increased progressively in the order Aksu < Qingdao < Tsukuba. Surface-sensitive XANES in the conversion electron yield mode (CEY) showed that the gypsum is formed selectively at the surface of mineral aerosols for all the samples except for that taken in Aksu during the dust period. The decrease of the [Gyp]/[Ca2+]t ratio with an increase in particle size showed that the neutralization effect proceeds from the particle surface. For the Aksu sample in the dust period, however, (i) the [Gyp]/[Ca2+]t ratios obtained by XANES measured in the fluorescence (FL; regarded as bulk analysis) and CEY modes were similar and (ii) size dependence was not found, showing that neutralization is not important for the sample because of the large supply of mineral aerosol with little neutralization effect in Aksu. It was also found that the pH of the aerosol and the ratio of (NH4)2SO4 to gypsum were positively and negatively correlated with the Ca (or calcite) content, respectively. The speciation of Ca by XANES revealed the neutralization processes of acidic sulfur species by calcite during the long-range transport of mineral aerosols. PMID:19764213

  18. Comparison of the magnetic properties of GeMn thin films through Mn L-edge x-ray absorption

    SciTech Connect

    Ahlers, S.; Stone, P.R.; Sircar, N.; Arenholz, E.; Dubon, O. D.; Bougeard, D.

    2009-08-04

    X-ray absorption spectroscopy of epitaxial GeMn thin films reveals an experimentally indistinguishable electronic configuration of Mn atoms incorporated in Ge{sub 1?x}Mn{sub x} nanoclusters and in precipitates of the intermetallic compound Mn{sub 5}Ge{sub 3}, respectively. However, the average magnetic response of thin films containing Ge{sub 1?x}Mn{sub x} nanoclusters is lower than the response of films containing Mn{sub 5}Ge{sub 3} precipitates. This reduced magnetic response of Ge{sub 1?x}Mn{sub x} nanoclusters is explained in terms of a fraction of Mn atoms being magnetically inactive due to antiferromagnetic coupling or the presence of structural disorder. A determination of the role of magnetically inactive Mn atoms in the self-assembly of the thermodynamically metastable Ge{sub 1?x}Mn{sub x} nanoclusters seems to be an essential ingredient for an enhanced control of this promising high Curie temperature magnetic semiconductor.

  19. Probing Variable Amine/Amide Ligation in NiIIN2S2 Complexes Using Sulfur K-Edge and Nickel L-Edge X-ray Absorption Spectroscopies: Implications for the Active Site of Nickel Superoxide Dismutase

    SciTech Connect

    Shearer,J.; Dehestani, A.; Abanda, F.

    2008-01-01

    Nickel superoxide dismutase (NiSOD) is a recently discovered metalloenzyme that catalyzes the disproportionation of O2* into O2 and H2O2. In its reduced state, the mononuclear NiII ion is ligated by two cis-cysteinate sulfurs, an amine nitrogen (from the protein N-terminus), and an amide nitrogen (from the peptide backbone). Unlike many small molecule and metallopeptide-based NiN2S2 complexes, S-based oxygenation is not observed in NiSOD. Herein we explore the spectroscopic properties of a series of three NiIIN2S2 complexes (bisamine-ligated (bmmp-dmed)NiII, amine/amide-ligated (NiII(BEAAM)), and bisamide-ligated (NiII(emi))2) with varying amine/amide ligation to determine the origin of the dioxygen stability of NiSOD. Ni L-edge X-ray absorption spectroscopy (XAS) demonstrates that there is a progression in ligand-field strength with (bmmp-dmed)NiII having the weakest ligand field and (NiII(emi)2) having the strongest ligand field. Furthermore, these Ni L-edge XAS studies also show that all three complexes are highly covalent with (NiII(BEEAM)) having the highest degree of metal-ligand covalency of the three compounds studied. S K-edge XAS also shows a high degree of NiS covalency in all three complexes. The electronic structures of the three complexes were probed using both hybrid-DFT and multiconfigurational SORCI calculations. These calculations demonstrate that the nucleophilic Ni(3d)/S()* HOMO of these NiN2S2 complexes progressively decreases in energy as the amide-nitrogens are replaced with amine nitrogens. This decrease in energy of the HOMO deactivates the Ni-center toward O2 reactivity. Thus, the NiS bond is protected from S-based oxygenation explaining the enhanced stability of the NiSOD active-site toward oxygenation by dioxygen.

  20. Acid-site characterization of water-oxidized alumina films by near-edge x-ray absorption and soft x-ray photoemission

    SciTech Connect

    O`Hagan, P.J.; Merrill, R.P.; Rhodin, T.N.; Woronick, S.W.; Shinn, N.D.; Woolery, G.L.; Chester, A.W.

    1994-12-01

    Hydroxylated alumina films have been synthesized by water oxidation of single crystal Al(110) surfaces. Thermal dehydroxylation results in anion vacancies which produce an Al(3s) defect state 3.5 eV below the conduction band edge. A maximum in the defect-DOS occurs for oxides heated to 350 to 400C, which is where the materials exhibit maximum Lewis acidity with respect to C{sub 2}H{sub 4}. Adsorbed C{sub 2}H{sub 4} produces thermally active C{sub 2} species which interact covalently with the defect-DOS and nonbonding O(2p) from the top of the valence band. C(1s) binding energies suggest significant charge transfer which is consistent with a carbenium ion. Ni evaporated onto the surface, however, transfers charge directly to Al species and does not interact with O atoms at the defect site. The defect-DOS is regenerated when the C{sub 2} species decomposes or when Ni migrates thermally through the oxide layer.

  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. Near-edge x-ray absorption studies of Na-doped tetracyanoethylene films: A model system for the V(TCNE)x room-temperature molecular magnet

    NASA Astrophysics Data System (ADS)

    Carlegrim, E.; Gao, B.; Kanciurzewska, A.; de Jong, M. P.; Wu, Z.; Luo, Y.; Fahlman, M.

    2008-02-01

    V(TCNE)x , with TCNE=tetracyanoethylene and xtilde 2 , is an organic-based molecular magnet with potential to be used in spintronic devices. With the aim of shedding light on the unoccupied frontier electronic structure of V(TCNE)x we have studied pristine TCNE and sodium-intercalated TCNE by near edge x-ray absorption fine structure (NEXAFS) spectroscopy as well as with theoretical calculations. Sodium-intercalated TCNE was used as a model system of the more complex V(TCNE)x and both experimental and theoretical results of the model compound have been used to interpret the NEXAFS spectra of V(TCNE)x . By comparing the experimental and theoretical C K -edge of pristine TCNE, the contributions from the various carbon species (cyano and vinyl) could be disentangled. Upon fully sodium intercalation, TCNE is n doped with one electron per molecule and the features in the C and N K -edge spectra of pristine TCNE undergo strong modification caused by partially filling the TCNE lowest unoccupied molecular orbital (LUMO). When comparing the C and N K -edge NEXAFS spectra of fully sodium-doped TCNE with V(TCNE)x , the spectra are similar except for broadening of the features which originates from structural disorder of the V(TCNE)x films. The combined results from the model system and V(TCNE)x suggest that the lowest unoccupied molecular orbital with density on the nitrogen atoms in V(TCNE)x has no significant hybridization with vanadium and is similar to the so-called singly occupied molecular orbital of the TCNE anion. This suggests that the LUMO of V(TCNE)x is TCNE- or vanadiumlike, in contrast to the frontier occupied electronic structure where the highest occupied molecular orbital is a hybridization between V(3d) and cyano carbons. The completely different nature of the unoccupied and occupied frontier electronic structure of the material will most likely affect both charge injection and transport properties of a spintronic device featuring V(TCNE)x .

  3. Strong interlayer coupling mediated giant two-photon absorption in MoS e2 /graphene oxide heterostructure: Quenching of exciton bands

    NASA Astrophysics Data System (ADS)

    Sharma, Rituraj; Aneesh, J.; Yadav, Rajesh Kumar; Sanda, Suresh; Barik, A. R.; Mishra, Ashish Kumar; Maji, Tuhin Kumar; Karmakar, Debjani; Adarsh, K. V.

    2016-04-01

    A complex few-layer MoS e2 /graphene oxide (GO) heterostructure with strong interlayer coupling was prepared by a facile hydrothermal method. In this strongly coupled heterostructure, we demonstrate a giant enhancement of two-photon absorption that is in stark contrast to the reverse saturable absorption of a weakly coupled MoS e2 /GO heterostructure and saturable absorption of isolated MoS e2 . Spectroscopic evidence of our study indicates that the optical signatures of isolated MoS e2 and GO domains are significantly modified in the heterostructure, displaying a direct coupling of both domains. Furthermore, our first-principles calculations indicate that strong interlayer coupling between the layers dramatically suppresses the MoS e2 excitonic bands. We envision that our findings provide a powerful tool to explore different optical functionalities as a function of interlayer coupling, which may be essential for the development of device technologies.

  4. Impurity-defect emission from undoped Cd1- x Zn x Te single crystals near the fundamental absorption edge

    NASA Astrophysics Data System (ADS)

    Krivobok, V. S.; Denisov, I. A.; Mozhevitina, E. N.; Nikolaev, S. N.; Onishchenko, E. E.; Pruchkina, A. A.; Silina, A. A.; Smirnova, N. A.; Chernopitsskii, M. A.; Shmatov, N. I.

    2016-05-01

    Shallow impurity-defect states in undoped Cd1- x Zn x Te ( x ˜ 3-6%) single crystals have been studied using low-temperature photoluminescence measurements. It has been found that the effect exerted by zinc is mainly reduced to a rigid shift of all the specific features associated with the exciton radiation, which made it possible, with a high (˜0.3 meV) accuracy, to measure the band gap and the zinc concentration in solid solutions. Hydrogen-like donors with the ground-state energy of ˜14 meV and four types of acceptors with average activation energies of 59.3 ± 0.6 meV, 69.6 ± 1.5 meV, 155.8 ± 2.0 meV, and 52.3 ± 0.6 meV have been identified in all the crystals studied. Based on a comparison with the results of the analysis of the impurity background and the data available in the literature on impurity-defect emission in undoped CdTe, the first three acceptors can be assigned to the substitutional impurities NaCd, PTe, and CuCd, respectively. The most shallow acceptor (52.3 ± 0.6 meV) is a complex defect in which there is a nonstandard excited level separated by only 7 meV from the ground level. This level is formed apparently due to the removal of degeneracy, which is characteristic of T D acceptors, by the low-symmetry potential of the complex defect.

  5. A study of the structure of the ν1(HF) absorption band of the СH3СN…HF complex

    NASA Astrophysics Data System (ADS)

    Gromova, E. I.; Glazachev, E. V.; Bulychev, V. P.; Koshevarnikov, A. M.; Tokhadze, K. G.

    2015-09-01

    The ν1(HF) absorption band shape of the CH3CN…HF complex is studied in the gas phase at a temperature of 293 K. The spectra of gas mixtures CH3CN/HF are recorded in the region of 4000-3400 cm-1 at a resolution from 0.1 to 0.005 cm-1 with a Bruker IFS-120 HR vacuum Fourier spectrometer in a cell 10 cm in length with wedge-shaped sapphire windows. The procedure used to separate the residual water absorption allows more than ten fine-structure bands to be recorded on the low-frequency wing of the ν1(HF) band. It is shown that the fine structure of the band is formed primarily due to hot transitions from excited states of the low-frequency ν7 librational vibration. Geometrical parameters of the equilibrium nuclear configuration, the binding energy, and the dipole moment of the complex are determined from a sufficiently accurate quantum-chemical calculation. The frequencies and intensities for a number of spectral transitions of this complex are obtained in the harmonic approximation and from variational solutions of anharmonic vibrational problems.

  6. A laboratory Atlas of the 5 nu-1 NH3 absorption band at 6475 A with applications to Jupiter and Saturn

    NASA Technical Reports Server (NTRS)

    Giver, L. P.; Miller, J. H.; Boese, R. W.

    1975-01-01

    A complete atlas of the 5 nu-1 absorption band of NH3 is presented together with measurements of the total band intensity, line intensities, and self-broadening coefficients. The spectrum, which is displayed in the interval from 6418 to 6550 A, was obtained photoelectrically at a pressure of 0.061 atm, and many more lines were seen in this spectrum than in a previous one obtained at a pressure of 0.39 atm. The band intensity is used to derive the NH3 abundance in the atmospheres of Jupiter and Saturn, and the abundances in a single vertical path are found to be about 10 m amagat for Jupiter and 2 m amagat for Saturn. These results are shown to be in agreement with previous results obtained from higher resolution photographic spectra.

  7. Complexities in pyroxene compositions derived from absorption band centers: Examples from Apollo samples, HED meteorites, synthetic pure pyroxenes, and remote sensing data

    NASA Astrophysics Data System (ADS)

    Moriarty, D. P.; Pieters, C. M.

    2016-02-01

    We reexamine the relationship between pyroxene composition and near-infrared absorption bands, integrating measurements of diverse natural and synthetic samples. We test an algorithm (PLC) involving a two-part linear continuum removal and parabolic fits to the 1 and 2 μm bands—a computationally simple approach which can easily be automated and applied to remote sensing data. Employing a suite of synthetic pure pyroxenes, the PLC technique is shown to derive similar band centers to the modified Gaussian model. PLC analyses are extended to natural pyroxene-bearing materials, including (1) bulk lunar basalts and pyroxene separates, (2) diverse lunar soils, and (3) HED meteorites. For natural pyroxenes, the relationship between composition and absorption band center differs from that of synthetic pyroxenes. These differences arise from complexities inherent in natural materials such as exsolution, zoning, mixing, and space weathering. For these reasons, band center measurements of natural pyroxene-bearing materials are compositionally nonunique and could represent three distinct scenarios (1) pyroxene with a narrow compositional range, (2) complexly zoned pyroxene grains, or (3) a mixture of multiple pyroxene (or nonpyroxene) components. Therefore, a universal quantitative relationship between band centers and pyroxene composition cannot be uniquely derived for natural pyroxene-bearing materials without additional geologic context. Nevertheless, useful relative relationships between composition and band center persist in most cases. These relationships are used to interpret M3 data from the Humboldtianum Basin. Four distinct compositional units are identified (1) Mare Humboldtianum basalts, (2) distinct outer basalts, (3) low-Ca pyroxene-bearing materials, and (4) feldspathic materials.

  8. Clay composition and swelling potential estimation of soils using depth of absorption bands in the SWIR (1100-2500 nm) spectral domain

    NASA Astrophysics Data System (ADS)

    Dufréchou, Grégory; Granjean, Gilles; Bourguignon, Anne

    2014-05-01

    Swelling soils contain clay minerals that change volume with water content and cause extensive and expensive damage on infrastructures. Presence of clay minerals is traditionally a good estimator of soils swelling and shrinking behavior. Montmorillonite (i.e. smectite group), illite, kaolinite are the most common minerals in soils and are usually associated to high, moderate, and low swelling potential when they are present in significant amount. Characterization of swelling potential and identification of clay minerals of soils using conventional analysis are slow, expensive, and does not permit integrated measurements. SWIR (1100-2500 nm) spectral domain are characterized by significant spectral absorption bands related to clay content that can be used to recognize main clay minerals. Hyperspectral laboratory using an ASD Fieldspec Pro spectrometer provides thus a rapid and less expensive field surface sensing that permits to measure soil spectral properties. This study presents a new laboratory reflectance spectroscopy method that used depth of clay diagnostic absorption bands (1400 nm, 1900 nm, and 2200 nm) to compare natural soils to synthetic montmorillonite-illite-kaolinite mixtures. We observe in mixtures that illite, montmorillonite, and kaolinite content respectively strongly influence the depth of absorption bands at 1400 nm (D1400), 1900 nm (D1900), and 2200 nm (D2200). To attenuate or removed effects of abundance and grain size, depth of absorption bands ratios were thus used to performed (i) 3D (using D1900/D2200, D1400/D1900, and D2200/D1400 as axis), and (ii) 2D (using D1400/D1900 and D1900/D2200 as axis) diagrams of synthetic mixtures. In this case we supposed that the overall reduction or growth of depth absorption bands should be similarly affected by the abundance and grain size of materials in soil. In 3D and 2D diagrams, the mixtures define a triangular shape formed by two clay minerals as external envelop and the three clay minerals mixtures

  9. 8-band k·p modelling of mid-infrared intersubband absorption in Ge quantum wells

    NASA Astrophysics Data System (ADS)

    Paul, D. J.

    2016-07-01

    The 8-band k.p parameters which include the direct band coupling between the conduction and the valence bands are derived and used to model optical intersubband transitions in Ge quantum well heterostructure material grown on Si substrates. Whilst for Si rich quantum wells the coupling between the conduction bands and valence bands is not important for accurate modelling, the present work demonstrates that the inclusion of such coupling is essential to accurately determine intersubband transitions between hole states in Ge and Ge-rich Si1-xGex quantum wells. This is due to the direct bandgap being far smaller in energy in Ge compared to Si. Compositional bowing parameters for a range of the key modelling input parameters required for Ge/SiGe heterostructures, including the Kane matrix elements, the effective mass of the Γ 2 ' conduction band, and the Dresselhaus parameters for both 6- and 8-band k.p modelling, have been determined. These have been used to understand valence band intersubband transitions in a range of Ge quantum well intersubband photodetector devices in the mid-infrared wavelength range.

  10. Tetrahalide Complexes of the [U(NR)(2)]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

    SciTech Connect

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

    2013-02-13

    Synthetic routes to salts containing uranium bisimido tetrahalide anions [U(NR)(2)X-4](2-) (X = Cl-, Br-) and non-coordinating NEt4+ and PPh4+ countercations are reported. In general, these compounds can be prepared from U(NR)(2)I-2(THF)(x) (x = 2 and R = 'Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl-, the [U(NMe)(2)](2 +) cation also reacts with Br- to form stable [NEt4](2)[U(NMe)(2)Br-4] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO2](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh4](2)[U((NBu)-Bu-t)(2)Cl-4] and [PPh4](2)[UO2Cl4]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  11. The iron-site structure of [Fe]-hydrogenase and model systems: an X-ray absorption near edge spectroscopy study†‡

    PubMed Central

    Salomone-Stagni, Marco; Stellato, Francesco; Whaley, C. Matthew; Vogt, Sonja; Morante, Silvia; Shima, Seigo; Rauchfuss, Thomas B.; Meyer-Klaucke, Wolfram

    2012-01-01

    The [Fe]-hydrogenase is an ideal system for studying the electronic properties of the low spin iron site that is common to the catalytic centres of all hydrogenases. Because they have no auxiliary iron-sulfur clusters and possess a cofactor containing a single iron centre, the [Fe]-hydrogenases are well suited for spectroscopic analysis of those factors required for the activation of molecular hydrogen. Specifically, in this study we shed light on the electronic and molecular structure of the iron centre by XAS analysis of [Fe]-hydrogenase from Methanocaldococcus jannashii and five model complexes (Fe(ethanedithiolate)-(CO)2(PMe3)2, [K(18-crown-6)]2[Fe(CN)2(CO)3], K[Fe(CN)(CO)4], K3[Fe(iii)(CN)6], K4[Fe(ii)(CN)6]). The different electron donors have a strong influence on the iron absorption K-edge energy position, which is frequently used to determine the metal oxidation state. Our results demonstrate that the K-edges of Fe(ii) complexes, achieved with low-spin ferrous thiolates, are consistent with a ferrous centre in the [Fe]-hydrogenase from Methanocaldococcus jannashii. The metal geometry also strongly influences the XANES and thus the electronic structure. Using in silico simulation, we were able to reproduce the main features of the XANES spectra and describe the effects of individual donor contributions on the spectra. Thereby, we reveal the essential role of an unusual carbon donor coming from an acyl group of the cofactor in the determination of the electronic structure required for the activity of the enzyme. PMID:20221540

  12. Iron L-edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin: Experimental Insight into Fe-O2 Bonding

    PubMed Central

    Wilson, Samuel A.; Kroll, Thomas; Decreau, Richard A.; Hocking, Rosalie K.; Lundberg, Marcus; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

    2013-01-01

    The electronic structure of the Fe–O2 center in oxy-hemoglobin and oxy-myoglobin is a long-standing issue in the field of bioinorganic chemistry. Spectroscopic studies have been complicated by the highly delocalized nature of the porphyrin and calculations require interpretation of multi-determinant wavefunctions for a highly covalent metal site. Here, iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction (VBCI) multiplet model, is applied to directly probe the electronic structure of the iron in the biomimetic Fe–O2 heme complex [Fe(pfp)(1-MeIm)O2] (pfp = meso-tetra(α,α,α,α-o-pivalamidophenyl) porphyrin or TpivPP). This method allows separate estimates of σ-donor, π-donor, and π-acceptor interactions through ligand to metal charge transfer (LMCT) and metal to ligand charge transfer (MLCT) mixing pathways. The L-edge spectrum of [Fe(pfp)(1-MeIm)O2] is further compared to those of [FeII(pfp)(1-MeIm)2], [FeII(pfp)], and [FeIII(tpp)(ImH)2]Cl (tpp = meso-tetraphenylporphyrin) which have FeII S = 0, FeII S = 1 and FeIII S = 1/2 ground states, respectively. These serve as references for the three possible contributions to the ground state of oxy-pfp. The Fe–O2 pfp site is experimentally determined to have both significant σ-donation and a strong π-interaction of the O2 with the iron, with the latter having implications with respect to the spin polarization of the ground state. PMID:23259487

  13. Alignment of the dye's molecular levels with the TiO2 band edges in dye-sensitized solar cells: a DFT TDDFT study

    NASA Astrophysics Data System (ADS)

    DeAngelis, Filippo; Fantacci, Simona; Selloni, Annabella

    2008-10-01

    We present a theoretical study of the lineup of the LUMO of Ru(II)-polypyridyl (N3 and N719) molecular dyes with the conduction band edge of a TiO2 anatase nanoparticle. We use density functional theory (DFT) and the Car-Parrinello scheme for efficient optimization of the dye-nanoparticle systems, followed by hybrid B3LYP functional calculations of the electronic structure and time-dependent DFT (TDDFT) determination of the lowest vertical excitation energies. The electronic structure and TDDFT calculations are performed in water solution, using a continuum model. Various approximate procedures to compute the excited state oxidation potential of dye sensitizers are discussed. Our calculations show that the level alignment for the interacting nanoparticle-sensitizer system is very similar, within about 0.1 eV, to that for the separated TiO2 and dye. The excellent agreement of our results with available experimental data indicates that the approach of this work could be used as an efficient predictive tool to help the optimization of dye-sensitized solar cells.

  14. Theoretical Study of L-Edge Resonant Inelastic X-ray Scattering in La2CuO4 on the Basis of Detailed Electronic Band Structure

    NASA Astrophysics Data System (ADS)

    Nomura, Takuji

    2015-09-01

    We study theoretically resonant inelastic x-ray scattering (RIXS) at the Cu L3-edge in a typical parent compound of high-Tc cuprate superconductors La2CuO4 on the basis of a detailed electronic band structure. We construct a realistic and precise tight-binding model by employing the maximally-localized Wannier functions derived from a first-principles electronic structure calculation, and then take account of the Coulomb repulsion between d electrons at each Cu site. The antiferromagnetic ground state is described within the Hartree-Fock approximation, and take account of electron correlations in the intermediate states of RIXS within the random-phase approximation (RPA). Calculated RIXS spectra agree well with the experimentally observed features including low-energy magnon excitation, d-d excitations, and charge-transfer excitations, over a wide excitation-energy range. In particular, we stress the importance of photon polarization dependence: the intensity of magnon excitation and the spectral structure of d-d excitations depend significantly not only on the polarization direction of incident incoming photons but also that of outgoing photons. It is demonstrated that the single-magnon excitation intensity is maximized when the polarization directions of incoming and outgoing photons are perpendicular to each other.

  15. 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.

  16. The Rovibrational Intensities of Five Absorption Bands of (12)C(16)O2 Between 5218 and 5349/cm

    NASA Technical Reports Server (NTRS)

    Giver, Lawrence P.; Brown, Linda R.; Chackerian, Charles, Jr.; Freedman, Richard S.; Gore, Warren J. (Technical Monitor)

    2002-01-01

    Absolute line intensities, band intensities, and Herman-Wallis parameters were measured for the (01(sup 1)2)(sub I) from (00(sup 0)0)(sub I) perpendicular band of (12)C(16)O2 centered at 5315/cm, along with the three nearby associated hot bands: (10(sup 0)2)(sub II) from (01(sup 1)0)(sub I) at 5248/cm, (02(sup 2))(sub I) from (01(sup 1)0)(sub I) at 5291/cm, and (10(sup 0)2)(sub I) from (01(sup 1)0)(sub I) at 5349/cm. The nearby parallel hot band (30(sup 0))(sub I) from (10(sup 0)0)(sub II) at 5218/cm was also included in this study.

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

    PubMed

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-08-01

    The C 1s and N 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of three prototype tetraphenyl porphyrin (TPP) molecules are discussed in the framework of a combined experimental and theoretical study. We employ time-dependent density-functional theory (TDDFT) to compute the NEXAFS spectra of the open- and closed-shell metalloporphyrins CoTPP and ZnTPP as well as the free-base 2HTPP in realistic nonplanar conformations. Using Becke's well-known half-and-half hybrid functional, the computed core excitation spectra are mostly in good agreement with the experimental data in the low-energy region below the appropriate ionization threshold. To make these calculations feasible, we apply a new, simple scheme based on TDDFT using a modified single-particle input spectrum. This scheme is very easy to implement in standard codes and allows one to compute core excitation spectra at a similar cost as ordinary UV/vis spectra even for larger molecules. We employ these calculations for a detailed assignment of the NEXAFS spectra including subtle shifts in certain peaks of the N 1s spectra, which depend on the central coordination of the TPP ligand. We furthermore assign the observed NEXAFS resonances to the individual molecular subunits of the investigated TPP molecules. PMID:20707545

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

    NASA Astrophysics Data System (ADS)

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-08-01

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

  19. Measurement of mass attenuation coefficients in some Cr, Co and Fe compounds around the absorption edge and the validity of the mixture rule

    NASA Astrophysics Data System (ADS)

    Turgut, U.; Simsek, O.; Büyükkasap, E.

    2007-08-01

    The total mass attenuation coefficients for elements Cr, Co and Fe and compounds CrCl_{2}, CrCl_{3}, Cr_{2}(SO_{4})_{3}K_{2}SO_{4}\\cdot24H_{2}O, CoO, CoCl_{2}, Co(CH_{3}COO)_{2}, FePO_{4}, FeCl_{3}\\cdot6H_{2}O, Fe(SO_{4})_{2}NH_{4}\\cdot12H_{2}O were measured at different energies between 4.508 and 14.142 keV using secondary excitation method. Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr were chosen as secondary exciters. 59.5 keV γ-rays emitted from a ^{241}Am annular source were used to excite a secondary exciter and K_{α}(K-L_{3}, L_{2}) lines emitted by the secondary exciter were counted by a Si(Li) detector with a resolution of 160 eV at 5.9 keV. It was observed that mixture rule method is not a suitable method for determination of the mass attenuation coefficients of compounds, especially at an energy that is near the absorption edge. The obtained values were compared with theoretical values.

  20. Aluminum incorporation in Ti{sub 1-x}Al{sub x}N films studied by x-ray absorption near-edge structure

    SciTech Connect

    Gago, R.; Redondo-Cubero, A.; Endrino, J. L.; Jimenez, I.; Shevchenko, N.

    2009-06-01

    The local bonding structure of titanium aluminum nitride (Ti{sub 1-x}Al{sub x}N) films grown by dc magnetron cosputtering with different AlN molar fractions (x) has been studied by x-ray absorption near-edge structure (XANES) recorded in total electron yield mode. Grazing incidence x-ray diffraction (GIXRD) shows the formation of a ternary solid solution with cubic structure (c-Ti{sub 1-x}Al{sub x}N) that shrinks with the incorporation of Al and that, above a solubility limit of xapprox0.7, segregation of w-AlN and c-Ti{sub 1-x}Al{sub x}N phases occurs. The Al incorporation in the cubic structure and lattice shrinkage can also be observed using XANES spectral features. However, contrary to GIXRD, direct evidence of w-AlN formation is not observed, suggesting a dominance and surface enrichment of cubic environments. For x>0.7, XANES shows the formation of Ti-Al bonds, which could be related to the segregation of w-AlN. This study shows the relevance of local-order information to assess the atomic structure of Ti{sub 1-x}Al{sub x}N solutions.