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Sample records for absorption near-edge spectra

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

  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. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

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

    SciTech Connect

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

    1996-07-01

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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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.

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

    SciTech Connect

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

    2009-10-21

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

  12. 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.

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

    SciTech Connect

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

    2015-05-07

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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

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

    NASA Astrophysics Data System (ADS)

    Gao, Yuan

    of multi-electron excitations being responsible for higher energy features in the XANES was investigated by comparing the energy loss satellites in the fluorine 1s x-ray photoelectron spectra with features at corresponding energies in the fluorine K edge absorption spectra. Finally the fluorine K edges in the rare-earth trifluorides LaF_3, CeF _3, NdF_3, SmF _3, EuF_3, DyF _3 and YbF_3 were explored for the first time with the high resolution x -ray absorption spectroscopy. The near edge part of the fluorine K edges in all seven rare-earth trifluorides was found not to be dominated by the Bragg peaks because of the short life time of the photoelectron and the low crystal symmetry.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  9. 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.

  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. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory.

    PubMed

    Myhre, Rolf H; Coriani, Sonia; Koch, Henrik

    2016-06-14

    Core excited states are challenging to calculate, mainly because they are embedded in a manifold of high-energy valence-excited states. However, their locality makes their determination ideal for local correlation methods. In this paper, we demonstrate the performance of multilevel coupled cluster theory in computing core spectra both within the core-valence separated and the asymmetric Lanczos implementations of coupled cluster linear response theory. We also propose a visualization tool to analyze the excitations using the difference between the ground-state and excited-state electron densities. PMID:27182829

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules

    SciTech Connect

    Kolczewski, C.; Puettner, R.; Martins, M.; Schlachter, A.S.; Snell, G.; Sant'Anna, M.M.; Hermann, K.; Kaindl, G.

    2006-01-21

    We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KLII&III, KLI) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

    SciTech Connect

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

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KLII&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&III and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at

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

    SciTech Connect

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

    1995-11-15

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

  20. 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.

  1. Probing the Ordering of Semiconducting Fluorene-Thiophene Copolymer Surfaces on Rubbed Polyimide Substrates by Near-Edge X-ray Absorption Fine Structure

    SciTech Connect

    Pattison,L.; Hexemer, A.; Kramer, E.; Krishnan, S.; Petroff, P.; Fischer, D.

    2006-01-01

    The temperature-dependent alignment of semiconducting liquid crystalline fluorene-thiophene copolymer (F8T2) thin film surfaces was investigated using the near-edge X-ray absorption fine structure (NEXAFS) technique. Partial electron yield spectra were recorded over a range of temperatures in order to observe directly the surface orientation as the polymer is heated and cooled through glass, crystal, and liquid crystal phases. In addition, samples annealed under varying processing conditions and quenched to room temperature were analyzed. The NEXAFS data show that (a) in thin F8T2 films at all temperatures the polymer backbone lies in the plane of the substrate, (b) the fluorene and thiophene rings are rotated randomly about the molecular axis, (c) orientation of the polymer backbone can be controlled using a rubbed polyimide alignment layer as a template for liquid crystal orientation, and (d) under proper annealing conditions there is strong temperature-dependent alignment of the copolymer main-chain axis to the rubbing direction which extends from the polyimide/F8T2 interface all the way to the F8T2 surface. The surface alignment does not disappear after annealing at temperatures {approx}30 K above the bulk nematic to isotropic transition.

  2. 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

  3. Point defects in hexagonal BN, BC{sub 3} and BC{sub x}N compounds studied by x-ray absorption near-edge structure

    SciTech Connect

    Caretti, Ignacio; Jimenez, Ignacio

    2011-07-15

    The generation of point defects in highly oriented pyrolytic boron nitride (HOPBN) after Ar{sup +} ion bombardment in ultrahigh vacuum and subsequent exposure to air was studied by angle-resolved x-ray absorption near edge structure (XANES). The pristine HOPBN showed well-oriented boron nitride (BN) basal planes parallel to the surface, with a negligible amount of defects. Amorphization of the BN structure took place after Ar{sup +} sputtering, as indicated by the broadening of the XANES spectra and significant decrease of the characteristic {pi}* states. Following air exposure, the XANES analysis revealed a spontaneous reorganization of the sample structure. The appearance of four new B1s {pi}* excitonic peaks indicates an oxygen decoration process of the nitrogen vacancies created by ion bombardment. A core-level shift model is presented to support this statement. This model is successfully extended to the case of oxygen substitutional defects in hexagonal BC{sub 3} and BC{sub x}N (0 < x < 4) materials, which can be applied to any B-based sp{sup 2}-bonded honeycomb structure.

  4. 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.

  5. 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

  6. 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.

  7. 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 .

  8. Novel Technique for Improving the Signal-to-Background Ratio of X-ray Absorption Near-Edge Structure Spectrum in Fluorescence Mode and Its Application to the Chemical State Analysis of Magnesium Doped in GaN

    NASA Astrophysics Data System (ADS)

    Yonemura, Takumi; Iihara, Junji; Saito, Yoshihiro; Ueno, Masaki

    2013-12-01

    A novel measurement technique for an X-ray absorption near-edge structure (XANES) for magnesium (Mg) doped in gallium nitride (GaN) has been developed. XANES spectra from Mg at very low concentrations of 1 ×1018/cm3 doped in GaN have successfully been obtained by optimizing the region of interest (ROI) and by using highly brilliant synchrotron radiation X-rays of SPring-8. The ROI is the limited energy region from an X-ray fluorescence spectrum to elicit signals of particular atoms. Using this new technique, we have investigated the effect of the annealing process for Mg-doped GaN on the XANES spectra. It has been found that the XANES spectra of Mg significantly changed as the annealing temperature increased. This indicates that the local structure around Mg atoms in GaN was modified by the annealing process.

  9. 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.

  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. 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.

  12. 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.

  13. 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

  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. 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.

  17. 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

  18. 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.

  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. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. Temperature dependent electronic structure of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film probed by X-ray absorption near edge structure

    SciTech Connect

    Zhang, Bangmin; Sun, Cheng-Jun E-mail: msecgm@nus.edu.sg; Heald, Steve M.; Chen, Jing-Sheng; Moog Chow, Gan E-mail: msecgm@nus.edu.sg; Venkatesan, T.

    2014-05-07

    The Mn K edge X-ray absorption near edge structures (XANES) of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film (100 nm) on (001) LaAlO{sub 3} substrate was measured at different temperatures to probe the MnO{sub 6} octahedron distortion and corresponding electronic structure. The absorption of high temperature paramagnetic-insulator phase differed from that of the low temperature ferromagnetic-metal phase. The temperature-dependent absorption intensity of Mn K edge XANES was correlated with the relaxation of distorted MnO{sub 6} octahedron, which changed the crystal field acting on the Mn site and the related electronic structure and properties. At low temperature, the splitting of Mn majority e{sub g} orbitals decreased and the density of states above the Fermi level increased in the relaxed MnO{sub 6} octahedron, as reflected by a wider separation between two sub-peaks in the pre-edge XANES spectra.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. X-ray absorption near-edge structure study on the configuration of Cu 2+ /histidine complexes at different pH values

    NASA Astrophysics Data System (ADS)

    Mei-Juan, Yu; Yu, Wang; Wei, Xu

    2016-04-01

    The local configurations around metal ions in metalloproteins are of great significance for understanding their biological functions. Cu2+/histidine (His) is a typical complex existing in many metalloproteins and plays an important role in lots of physiological functions. The three-dimensional (3D) structural configurations of Cu2+/His complexes at different pH values (2.5, 6.5, and 8.5) are quantitatively determined by x-ray absorption near-edge structure (XANES). Generally Cu2+/His complex keeps an octahedral configuration consisting of oxygen atoms from water molecules and oxygen or nitrogen atoms from histidine molecules coordinated around Cu2+. It is proved in this work that the oxygen atoms from water molecules, when increasing the pH value from acid to basic value, are gradually substituted by the Ocarboxyl, Nam, and Nim from hisitidine molecules. Furthermore, the symmetries of Cu2+/His complexes at pH 6.5 and pH 8.5 are found to be lower than at pH 2.5. Project supported by the National Natural Science Foundation of China (Grant No. 11205186).

  11. A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements.

    PubMed

    Seidler, G T; Mortensen, D R; Remesnik, A J; Pacold, J I; Ball, N A; Barry, N; Styczinski, M; Hoidn, O R

    2014-11-01

    We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low power x-ray (bremsstrahlung) tube source, a spherically bent crystal analyzer, and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of ∼5 keV to ∼10 keV while also demonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy comparable to those achieved at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure, the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-power line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 10(6)-10(7) photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based hard x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species. PMID:25430123

  12. In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

    PubMed

    Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

    2014-10-22

    Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB. PMID:25191695

  13. 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.

  14. A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements

    SciTech Connect

    Seidler, G. T. Mortensen, D. R.; Remesnik, A. J.; Pacold, J. I.; Ball, N. A.; Barry, N.; Styczinski, M.; Hoidn, O. R.

    2014-11-15

    We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low power x-ray (bremsstrahlung) tube source, a spherically bent crystal analyzer, and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of ∼5 keV to ∼10 keV while also demonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy comparable to those achieved at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure, the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-power line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 10{sup 6}–10{sup 7} photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based hard x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species.

  15. Understanding conversion mechanism of NiO anodic materials for Li-ion battery using in situ X-ray absorption near edge structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Jang, Jue-Hyuk; Chae, Byung-Mok; Oh, Hyun-Jung; Lee, Yong-Kul

    2016-02-01

    Nano-scaled NiO particles (nano-NiO) are prepared by a ligand stabilization method and compared with micron-sized NiO particles (micro-NiO) as anodic material of Li-ion battery. The structural and physical properties are characterized by N2 physisorption, transmission electron microscopy, and X-ray diffraction. The nano-NiO shows uniform spheres with an average particle size of 9 nm with high and stable discharge capacity of 637 mAh g-1, while the micro-NiO forms irregularly shaped particles with an average particle size of 750 nm with low capacity of 431 mAh g-1 at 0.5C. In situ X-ray absorption near edge structure (XANES) analysis reveals that the capacity and reversibility of the NiO anode is highly affected by the particle size of the NiO. The micro-NiO exhibits a low capacity with absence of phase transformation upon the discharge/charge cycles. In contrast, the nano-NiO exhibits a high capacity with reversible phase transformation between NiO and Ni metal upon the cycle test.

  16. A setup for synchrotron-radiation-induced total reflection X-ray fluorescence and X-ray absorption near-edge structure recently commissioned at BESSY II BAMline.

    PubMed

    Fittschen, U; Guilherme, A; Böttger, S; Rosenberg, D; Menzel, M; Jansen, W; Busker, M; Gotlib, Z P; Radtke, M; Riesemeier, H; Wobrauschek, P; Streli, C

    2016-05-01

    An automatic sample changer chamber for total reflection X-ray fluorescence (TXRF) and X-ray absorption near-edge structure (XANES) analysis in TXRF geometry was successfully set up at the BAMline at BESSY II. TXRF and TXRF-XANES are valuable tools for elemental determination and speciation, especially where sample amounts are limited (<1 mg) and concentrations are low (ng ml(-1) to µg ml(-1)). TXRF requires a well defined geometry regarding the reflecting surface of a sample carrier and the synchrotron beam. The newly installed chamber allows for reliable sample positioning, remote sample changing and evacuation of the fluorescence beam path. The chamber was successfully used showing accurate determination of elemental amounts in the certified reference material NIST water 1640. Low limits of detection of less than 100 fg absolute (10 pg ml(-1)) for Ni were found. TXRF-XANES on different Re species was applied. An unknown species of Re was found to be Re in the +7 oxidation state. PMID:27140163

  17. Synchrotron-based X-ray absorption near-edge spectroscopy imaging for laterally resolved speciation of selenium in fresh roots and leaves of wheat and rice

    PubMed Central

    Wang, Peng; Menzies, Neal W.; Lombi, Enzo; McKenna, Brigid A.; James, Simon; Tang, Caixian; Kopittke, Peter M.

    2015-01-01

    Knowledge of the distribution of selenium (Se) species within plant tissues will assist in understanding the mechanisms of Se uptake and translocation, but in situ analysis of fresh and highly hydrated plant tissues is challenging. Using synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide laterally resolved data, the speciation of Se in fresh roots and leaves of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) supplied with 1 μM of either selenate or selenite was investigated. For plant roots exposed to selenate, the majority of the Se was efficiently converted to C-Se-C compounds (i.e. methylselenocysteine or selenomethionine) as selenate was transported radially through the root cylinder. Indeed, even in the rhizodermis which is exposed directly to the bulk solution, only 12–31% of the Se was present as uncomplexed selenate. The C-Se-C compounds were probably sequestered within the roots, whilst much of the remaining uncomplexed Se was translocated to the leaves—selenate accounting for 52–56% of the total Se in the leaves. In a similar manner, for plants exposed to selenite, the Se was efficiently converted to C-Se-C compounds within the roots, with only a small proportion of uncomplexed selenite observed within the outer root tissues. This resulted in a substantial decrease in translocation of Se from the roots to leaves of selenite-exposed plants. This study provides important information for understanding the mechanisms responsible for the uptake and subsequent transformation of Se in plants. PMID:26019258

  18. Near-Edge X-ray Absorption Fine Structure Imaging of Spherical and Flat Counterfaces of Ultrananocrystalline Diamond Tribological Contacts: A Correlation of Surface Chemistry and Friction

    SciTech Connect

    A Konicek; C Jaye; M Hamilton; W Sawyer; D Fischer; R Carpick

    2011-12-31

    A recently installed synchrotron radiation near-edge X-ray absorption fine structure (NEXAFS) full field imaging electron spectrometer was used to spatially resolve the chemical changes of both counterfaces from an ultra-nanocrystalline diamond (UNCD) tribological contact. A silicon flat and Si{sub 3}N{sub 4} sphere were both coated with UNCD, and employed to form two wear tracks on the flat in a linear reciprocating tribometer. The first wear track was produced using a new, unconditioned sphere whose surface was thus conditioned during this first experiment. This led to faster run-in and lower friction when producing a second wear track using the conditioned sphere. The large depth of field of the magnetically guided NEXAFS imaging detector enabled rapid, large area spectromicroscopic imaging of both the spherical and flat surfaces. Laterally resolved NEXAFS data from the tribological contact area revealed that both substrates had an as-grown surface layer that contained a higher fraction of sp{sup 2}-bonded carbon and oxygen which was mechanically removed. Unlike the flat, the film on the sphere showed evidence of having graphitic character, both before and after sliding. These results show that the graphitic character of the sphere is not solely responsible for low friction and short run-in. Rather, conditioning the sphere, likely by removing asperities and passivating dangling bonds, leads to lower friction with less chemical modification of the substrate in subsequent tests. The new NEXAFS imaging spectroscopy detector enabled a more complete understanding of the tribological phenomena by imaging, for the first time, the surface chemistry of the spherical counterface which had been in continual contact during wear track formation.

  19. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for mapping nano-scale distribution of organic carbon forms in soil: Application to black carbon particles

    NASA Astrophysics Data System (ADS)

    Lehmann, Johannes; Liang, Biqing; Solomon, Dawit; Lerotic, Mirna; LuizãO, Flavio; Kinyangi, James; SchäFer, Thorsten; Wirick, Sue; Jacobsen, Chris

    2005-03-01

    Small-scale heterogeneity of organic carbon (C) forms in soils is poorly quantified since appropriate analytical techniques were not available up to now. Specifically, tools for the identification of functional groups on the surface of micrometer-sized black C particles were not available up to now. Scanning Transmission X-ray Microscopy (STXM) using synchrotron radiation was used in conjunction with Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy to investigate nano-scale distribution (50-nm resolution) of C forms in black C particles and compared to synchrotron-based FTIR spectroscopy. A new embedding technique was developed that did not build on a C-based embedding medium and did not pose the risk of heat damage to the sample. Elemental sulfur (S) was melted to 220°C until it polymerized and quenched with liquid N2 to obtain a very viscous plastic S in which the black C could be embedded until it hardened to a noncrystalline state and was ultrasectioned. Principal component and cluster analysis followed by singular value decomposition was able to resolve distinct areas in a black carbon particle. The core of the studied biomass-derived black C particles was highly aromatic even after thousands of years of exposure in soil and resembled the spectral characteristics of fresh charcoal. Surrounding this core and on the surface of the black C particle, however, much larger proportions of carboxylic and phenolic C forms were identified that were spatially and structurally distinct from the core of the particle. Cluster analysis provided evidence for both oxidation of the black C particle itself as well as adsorption of non-black C. NEXAFS spectroscopy has great potential to allow new insight into black C properties with important implications for biogeochemical cycles such as mineralization of black C in soils and sediments, and adsorption of C, nutrients, and pollutants as well as transport in the geosphere, hydrosphere, and atmosphere.

  20. 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.

  1. 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

  2. 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

  3. Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Willey, T; Willey, T

    2004-03-24

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the mechanically attached

  4. Characterization of functionalized self-assembled monolayers and surface-attached interlocking molecules using near-edge X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Willey, Trevor Michael

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a "molecular riveting" step to hold the mechanically attached

  5. 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

  6. X-ray absorption near-edge structures of LiMn2O4 and LiNi0.5Mn1.5O4 spinel oxides for lithium-ion batteries: the first-principles calculation study.

    PubMed

    Okumura, Toyoki; Yamaguchi, Yoichi; Kobayashi, Hironori

    2016-07-21

    Experimental Mn and Ni K-edge X-ray absorption near-edge structure (XANES) spectra were well reproduced for 5 V-class LixNi0.5Mn1.5O4 spinels as well as 4 V-class LixMn2O4 spinels using density functional theory. Local environmental changes around the Mn or Ni centres due to differences in the locations of Li ions and/or phase transitions in the spinel oxides were found to be very important contributors to the XANES shapes, in addition to the valence states of the metal ions. PMID:27333155

  7. Thermo-Active Behavior of Ethylene-Vinyl Acetate | Multiwall Carbon Nanotube Composites Examined by in Situ near-Edge X-ray Absorption Fine-Structure Spectroscopy

    PubMed Central

    2015-01-01

    NEXAFS spectroscopy was used to investigate the temperature dependence of thermally active ethylene-vinyl acetate | multiwall carbon nanotube (EVA|MWCNT) films. The data shows systematic variations of intensities with increasing temperature. Molecular orbital assignment of interplaying intensities identified the 1s → π*C=C and 1s → π*C=O transitions as the main actors during temperature variation. Furthermore, enhanced near-edge interplay was observed in prestrained composites. Because macroscopic observations confirmed enhanced thermal-mechanical actuation in prestrained composites, our findings suggest that the interplay of C=C and C=O π orbitals may be instrumental to actuation. PMID:24803975

  8. Thin Film Structure of Tetraceno[2,3-B]thiophene Characterized By Grazing Incidence X-Ray Scattering And Near-Edge X-Ray Absorption Fine Structure Analysis

    SciTech Connect

    Yuan, Q.; Mannsfeld, S.C.B.; Tang, M.L.; Toney, M.F.; Luening, J.; Bao, Z.A.; /Stanford U., Chem. Eng. /SLAC, SSRL

    2009-05-11

    Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on

  9. 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

  10. Study on the d state of platinum in Pt/SiO sub 2 and Na/Pt/SiO sub 2 catalysts under C double bond C hydrogenation conditions by X-ray absorption near-edge structure spectroscopy

    SciTech Connect

    Yoshitake, Hideaki; Iwasawa, Yasuhiro )

    1991-09-19

    The change in the d-electron density of platinum during D{sub 2} + CH{sub 2}{double bond}CHX reactions on Pt/SiO{sub 2} and Na/Pt/SiO{sub 2} catalysts and its influence on the catalysis were studied by X-ray absorption near-edge structure (XANES) spectroscopy, kinetics and FT-IR. It was demonstrated from the change of the white lines in XANES spectra at Pt L{sub 2} and L{sub 3} edges that CH{sub 2}{double bond}CHX (X = H, CH{sub 3}, COCH{sub 3}, CF{sub 3}, and CN) is adsorbed on the Pt surface and extracts the electrons of the d state. Hence, the deuterogenation rate is reduced as the value of Hammett's {sigma}{sub P} increases. The linear free energy relationship between the reaction rate and {sigma}{sub P} was observed for the deuterogenation of CH{sub 2}{double bond}CHX. The rate of ethene deuterogenation was promoted by Na{sub 2}O addition. The electron density of unoccupied d states of pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. The electron density of unoccupied d states of Pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. However, most of these additional electrons were observed to move to ethene under reaction conditions. The acceptor of the electrons was suggested by di-{sigma}-ethene by the shift of {upsilon}(C-H). The kinetic parameters are discussed in relation to the change in the d state of Pt as a function of {sigma}{sub P} and Na quantity.

  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. 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.

  13. Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

    PubMed

    De Brier, Niels; Gomand, Sara V; Donner, Erica; Paterson, David; Smolders, Erik; Delcour, Jan A; Lombi, Enzo

    2016-08-01

    Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition μ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility. PMID:27038325

  14. 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.

  15. Local structure of epitaxial GeTe and Ge2Sb2Te5 films grown on InAs and Si substrates with (100) and (111) orientations: An x-ray absorption near-edge structure study

    NASA Astrophysics Data System (ADS)

    Kolobov, A. V.; Fons, P.; Krbal, M.; Tominaga, J.; Giussani, A.; Perumal, K.; Riechert, H.; Calarco, R.; Uruga, T.

    2015-03-01

    GeTe is an end-point of the GeTe-Sb2Te3 quasibinary alloys often referred to as phase-change memory materials. The polycrystalline nature of the crystalline films used in devices and the concomitant presence of grain boundaries complicate detailed structural studies of the local structure. Recent progress in the epitaxial growth of phase-change materials offers unique possibilities for precise structural investigations. In this work, we report on results of x-ray absorption near-edge structure (XANES) studies of GeTe and Ge2Sb2Te5 epitaxial films grown on Si and InAs substrates with (100) and (111) orientations. The results show a strong dependence of the local structure on the substrate material and especially orientation and are discussed in conjunction with polycrystalline samples and ab-initio XANES simulations.

  16. Diurnal Variation and Spatial Distribution Effects on Sulfur Speciation in Aerosol Samples as Assessed by X-Ray Absorption Near-Edge Structure (XANES)

    PubMed Central

    Pongpiachan, Siwatt; Thumanu, Kanjana; Na Pattalung, Warangkana; Hirunyatrakul, Phoosak; Kittikoon, Itthipon; Ho, Kin Fai; Cao, Junji

    2012-01-01

    This paper focuses on providing new results relating to the impacts of Diurnal variation, Vertical distribution, and Emission source on sulfur K-edge XANES spectrum of aerosol samples. All aerosol samples used in the diurnal variation experiment were preserved using anoxic preservation stainless cylinders (APSCs) and pressure-controlled glove boxes (PCGBs), which were specially designed to prevent oxidation of the sulfur states in PM10. Further investigation of sulfur K-edge XANES spectra revealed that PM10 samples were dominated by S(VI), even when preserved in anoxic conditions. The “Emission source effect” on the sulfur oxidation state of PM10 was examined by comparing sulfur K-edge XANES spectra collected from various emission sources in southern Thailand, while “Vertical distribution effects” on the sulfur oxidation state of PM10 were made with samples collected from three different altitudes from rooftops of the highest buildings in three major cities in Thailand. The analytical results have demonstrated that neither “Emission source” nor “Vertical distribution” appreciably contribute to the characteristic fingerprint of sulfur K-edge XANES spectrum in PM10. PMID:22988545

  17. 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.

  18. Effects of strain relaxation in Pr0.67Sr0.33MnO3 films probed by polarization dependent X-ray absorption near edge structure

    PubMed Central

    Zhang, Bangmin; Chen, Jingsheng; Yang, Ping; Chi, Xiao; Lin, Weinan; Venkatesan, T.; Sun, Cheng-Jun; Heald, Steve M.; Chow, Gan Moog

    2016-01-01

    The Mn K edge X-ray absorption near edge structure (XANES) of Pr0.67Sr0.33MnO3 films with different thicknesses on (001) LaAlO3 substrate was measured, and the effects of strain relaxation on film properties were investigated. The films showed in-plane compressive and out-of-plane tensile strains. Strain relaxation occurred with increasing film thickness, affecting both lattice constant and MnO6 octahedral rotation. In polarization dependent XANES measurements using in-plane (parallel) and out-of-plane (perpendicular) geometries, the different values of absorption resonance energy Er confirmed the film anisotropy. The values of Er along these two directions shifted towards each other with increasing film thickness. Correlating with X-ray diffraction (XRD) results it is suggested that the strain relaxation decreased the local anisotropy and corresponding probability of electronic charge transfer between Mn 3d and O 2p orbitals along the in-plane and out-of-plane directions. The XANES results were used to explain the film-thickness dependent magnetic and transport properties. PMID:26818583

  19. Effects of strain relaxation in Pr0.67Sr0.33MnO3 films probed by polarization dependent X-ray absorption near edge structure

    DOE PAGESBeta

    zhang, Bangmin; Chen, Jingsheng; Venkatesan, T.; Sun, Cheng -Jun; Heald, Steve M.; Chow, Gan Moog; Yang, Ping; Chi, Xiao; Lin, Weinan

    2016-01-28

    In this study, the Mn K edge X-ray absorption near edge structure (XANES) of Pr0.67Sr0.33MnO3 films with different thicknesses on (001) LaAlO3 substrate were measured, and the effects of strain relaxation on film properties were investigated. The films experienced in-plane compressive strain and out-of-plane tensile strain. Strain relaxation evolved with the film thickness. In the polarization dependent XANES measurements, the in-plane (parallel) and out-of-plane (perpendicular) XANES spectrocopies were anisotropic with different absorption energy Er. The resonance energy Er along two directions shifted towards each other with increasing film thickness. Based on the X-ray diffraction results, it was suggested that themore » strain relaxation weakened the difference of the local environment and probability of electronic charge transfer (between Mn 3d and O 2p orbitals) along the in-plane and out-of-plane directions, which was responsible for the change of Er. XANES is a useful tool to probe the electronic structures, of which the effects on magnetic properties with the strain relaxation was also been studied.« less

  20. Effects of strain relaxation in Pr0.67Sr0.33MnO3 films probed by polarization dependent X-ray absorption near edge structure.

    PubMed

    Zhang, Bangmin; Chen, Jingsheng; Yang, Ping; Chi, Xiao; Lin, Weinan; Venkatesan, T; Sun, Cheng-Jun; Heald, Steve M; Chow, Gan Moog

    2016-01-01

    The Mn K edge X-ray absorption near edge structure (XANES) of Pr0.67Sr0.33MnO3 films with different thicknesses on (001) LaAlO3 substrate was measured, and the effects of strain relaxation on film properties were investigated. The films showed in-plane compressive and out-of-plane tensile strains. Strain relaxation occurred with increasing film thickness, affecting both lattice constant and MnO6 octahedral rotation. In polarization dependent XANES measurements using in-plane (parallel) and out-of-plane (perpendicular) geometries, the different values of absorption resonance energy Er confirmed the film anisotropy. The values of Er along these two directions shifted towards each other with increasing film thickness. Correlating with X-ray diffraction (XRD) results it is suggested that the strain relaxation decreased the local anisotropy and corresponding probability of electronic charge transfer between Mn 3d and O 2p orbitals along the in-plane and out-of-plane directions. The XANES results were used to explain the film-thickness dependent magnetic and transport properties. PMID:26818583

  1. [Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

    PubMed

    Shen, Ya-Ting

    2014-03-01

    In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability. PMID:25208420

  2. Interrogation of Surface, Skin, and Core Orientation in Thermotropic Liquid-Crystalline Copolyester Moldings by Near-Edge X-ray Absorption Fine Structure and Wide-Angle X-ray Scattering

    SciTech Connect

    Rendon,S.; Bubeck, R.; Thomas, L.; Burghardt, W.; Hexemer, A.; Fischer, D.

    2007-01-01

    Injection molding thermotropic liquid-crystalline polymers (TLCPs) usually results in the fabrication of molded articles that possess complex states of orientation that vary greatly as a function of thickness. 'Skin-core' morphologies are often observed in TLCP moldings. Given that both 'core' and 'skin' orientation states may often differ both in magnitude and direction, deconvolution of these complex orientation states requires a method to separately characterize molecular orientation in the surface region. A combination of two-dimensional wide-angle X-ray scattering (WAXS) in transmission and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to probe the molecular orientation in injection molded plaques fabricated from a 4,4'-dihydroxy-{alpha}-methylstilbene (DH{alpha}MS)-based thermotropic liquid crystalline copolyester. Partial electron yield (PEY) mode NEXAFS is a noninvasive ex situ characterization tool with exquisite surface sensitivity that samples to a depth of 2 nm. The effects of plaque geometry and injection molding processing conditions on surface orientation in the regions on- and off- axis to the centerline of injection molded plaques are presented and discussed. Quantitative comparisons are made between orientation parameters obtained by NEXAFS and those from 2D WAXS in transmission, which are dominated by the microstructure in the skin and core regions. Some qualitative comparisons are also made with 2D WAXS results from the literature.

  3. Structure analyses using X-ray photoelectron spectroscopy and X-ray absorption near edge structure for amorphous MS3 (M: Ti, Mo) electrodes in all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Matsuyama, Takuya; Deguchi, Minako; Mitsuhara, Kei; Ohta, Toshiaki; Mori, Takuya; Orikasa, Yuki; Uchimoto, Yoshiharu; Kowada, Yoshiyuki; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2016-05-01

    Electronic structure changes of sulfurs in amorphous TiS3 and MoS3 for positive electrodes of all-solid-state lithium batteries are examined by X-ray photoelectron spectroscopy (XPS) and the X-ray absorption near edge structure (XANES). The all-solid-state cell with amorphous TiS3 electrode shows the reversible capacity of about 510 mAh g-1 for 10 cycles with sulfur-redox in amorphous TiS3 during charge-discharge process. On the other hand, the cell with amorphous MoS3 shows the 1st reversible capacity of about 720 mAh g-1. The obtained capacity is based on the redox of both sulfur and molybdenum in amorphous MoS3. The irreversible capacity of about 50 mAh g-1 is observed at the 1st cycle, which is attributed to the irreversible electronic structure change of sulfur during the 1st cycle. The electronic structure of sulfur in amorphous MoS3 after the 10th charge is similar to that after the 1st charge. Therefore, the all-solid-state cell with amorphous MoS3 electrode shows relatively good cyclability after the 1st cycle.

  4. 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.

  5. Surface and in-depth characterization of lithium-ion battery cathodes at different cycle states using confocal micro-X-ray fluorescence-X-ray absorption near edge structure analysis

    NASA Astrophysics Data System (ADS)

    Menzel, Magnus; Schlifke, Annalena; Falk, Mareike; Janek, Jürgen; Fröba, Michael; Fittschen, Ursula Elisabeth Adriane

    2013-07-01

    The cathode material LiNi0.5Mn1.5O4 for lithium-ion batteries has been studied with confocal micro-X-ray fluorescence (CMXRF) combined with X-ray absorption near edge structure (XANES) at the Mn-K edge and the Ni-K edge. This technique allows for a non-destructive, spatially resolved (x, y and z) investigation of the oxidation states of surface areas and to some extent of deeper layers of the electrode. Until now CMXRF-XANES has been applied to a limited number of applications, mainly geo-science. Here, we introduce this technique to material science applications and show its performance to study a part of a working system. A novel mesoporous LiNi0.5Mn1.5O4 material was cycled (charged and discharged) to investigate the effects on the oxidation states at the cathode/electrolyte interface. With this approach the degradation of Mn3 + to Mn4 + only observable at the surface of the electrode could be directly shown. The spatially resolved non-destructive analysis provides knowledge helpful for further understanding of deterioration and the development of high voltage battery materials, because of its nondestructive nature it will be also suitable to monitor processes during battery cycling.

  6. Effect of heat treatment on the activity and stability of PtCo/C catalyst and application of in-situ X-ray absorption near edge structure for proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Lin, Rui; Zhao, Tiantian; Shang, Mingfeng; Wang, Jianqiang; Tang, Wenchao; Guterman, Vladimir E.; Ma, Jianxin

    2015-10-01

    For the purpose of reducing the cost and improving the performance of the proton exchange membrane fuel cell (PEMFC), some low-Pt or non-Pt catalysts have been studied in recent years. PtCo/C electrocatalysts are synthesized by a two-step reduction approach followed by the heat treatment. PtCo metal particles are uniformly dispersed on the surface of XC-72 carbon support, with a uniform particle size distribution. The PtCo/C catalyst after 400 °C heat treatment has the best electrochemical performance among the as-prepared catalysts, even superior to the commercial Pt/C catalyst. In the durability test, PtCo/C-400 also shows excellent stability with only 6.9% decline of electrochemical surface area (ECSA) after 1000 cyclic voltammetry (CV) cycles. In-situ X-ray absorption near edge structure (XANES) technique is conducted to explore the nanostructure change of Pt during the PEMFC operation. For PtCo/C catalyst, with the fuel cell operation potential decreasing from open circuit voltage (OCV) to 0.3 V, the Pt L3 white line intensity decreases continuously, indicating the decline of Pt 5d-vacancy due to the adsorption of oxygenated species.

  7. 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

  8. Creating semiconductor metafilms with designer absorption spectra

    PubMed Central

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

    2015-01-01

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

  9. Creating semiconductor metafilms with designer absorption spectra

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  10. Creating semiconductor metafilms with designer absorption spectra.

    PubMed

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

    2015-01-01

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

  11. pH-dependent x-ray absorption spectra of aqueous boron oxides

    NASA Astrophysics Data System (ADS)

    Duffin, Andrew M.; Schwartz, Craig P.; England, Alice H.; Uejio, Janel S.; Prendergast, David; Saykally, Richard J.

    2011-04-01

    Near edge x-ray absorption fine structure (NEXAFS) spectra at the boron K-edge were measured for aqueous boric acid, borate, and polyborate ions, using liquid microjet technology, and compared with simulated spectra calculated from first principles density functional theory in the excited electron and core hole (XCH) approximation. Thermal motion in both hydrated and isolated molecules was incorporated into the calculations by sampling trajectories from quantum mechanics/molecular mechanics simulations at the experimental temperature. The boron oxide molecules exhibit little spectral change upon hydration, relative to mineral samples. Simulations reveal that water is arranged nearly isotropically around boric acid and sodium borate, but the calculations also indicate that the boron K-edge NEXAFS spectra are insensitive to hydrogen bonding, molecular environment, or salt interactions.

  12. Absorption spectra of cold dilute solid solutions

    SciTech Connect

    Holland, R.F.; Maier, W.B. II; Freund, S.; Beattie, W.H.

    1983-06-01

    Infrared absorption spectra have been obtained for some compounds trapped in crystalline solids by freezing liquid Xe, Kr, Ar, or CH/sub 4/ solutions. The optical quality of the solid solutions is good, and they have been cooled to approx.80 K in 1.35 cm sample thicknesses to study the absorption in fundamental vibrational bands of the solutes. In the cases discussed, the bands are narrow, with observed full widths at half-maximum absorbance 0.05--0.30 cm/sup -1/ greater than the instrumental resolution (0.18--0.29 cm/sup -1/). The spectra appear to be free of ''multiple site'' and solute aggregate absorptions. Spectra displaying isotropic splitting in bands of natural BCl/sub 3/, SeF/sub 6/, OsO/sub 4/, TiCl/sub 4/, and MoF/sub 6/ are presented, and band frequencies are compared with some results obtained in evaporative matrices, in the gas phase, and in liquid solutions. For this comparison we have obtained some spectra of SeF/sub 6/ and BCl/sub 3/ gas.

  13. Absorption Features in Soil Spectra Assessment.

    PubMed

    Vašát, Radim; Kodešová, Radka; Borůvka, Luboš; Jakšík, Ondřej; Klement, Aleš; Drábek, Ondřej

    2015-12-01

    From a wide range of techniques appropriate to relate spectra measurements with soil properties, partial least squares (PLS) regression and support vector machines (SVM) are most commonly used. This is due to their predictive power and the availability of software tools. Both represent exclusively statistically based approaches and, as such, benefit from multiple responses of soil material in the spectrum. However, physical-based approaches that focus only on a single spectral feature, such as simple linear regression using selected continuum-removed spectra values as a predictor variable, often provide accurate estimates. Furthermore, if this approach extends to multiple cases by taking into account three basic absorption feature parameters (area, width, and depth) of all occurring features as predictors and subjecting them to best subset selection, one can achieve even higher prediction accuracy compared with PLS regression. Here, we attempt to further extend this approach by adding two additional absorption feature parameters (left and right side area), as they can be important diagnostic markers, too. As a result, we achieved higher prediction accuracy compared with PLS regression and SVM for exchangeable soil pH, slightly higher or comparable for dithionite-citrate and ammonium oxalate extractable Fe and Mn forms, but slightly worse for oxidizable carbon content. Therefore, we suggest incorporating the multiple linear regression approach based on absorption feature parameters into existing working practices. PMID:26555184

  14. Millimeter wave absorption spectra of biological samples

    SciTech Connect

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

    1980-01-01

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

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

    SciTech Connect

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

    2010-07-20

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

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

    PubMed Central

    Derricotte, Wallace D.; Evangelista, Francesco A.

    2015-01-01

    Orthogonality constrained density functional theory (OCDFT) is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree–Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine. PMID:25690350

  17. Optical absorption spectra of dications of carotenoids

    SciTech Connect

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

    1996-04-04

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

  18. Absorption spectra of irradiated XRCT radiochromic film

    NASA Astrophysics Data System (ADS)

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

    2006-06-01

    Gafchromic XRCT radiochromic film is a self-developing high sensitivity radiochromic film product which can be used for assessment of delivered radiation doses which could match applications such as computed tomography (CT) dosimetry. The film automatically changes colour upon irradiation changing from a yellow to green/brown colour. The absorption spectra of Gafchromic XRCT radiochromic film as measured with reflectance spectrophotometry have been investigated to analyse the dosimetry characteristics of the film. Results show two main absorption peaks produced from irradiation located at 636 nm and 585 nm. This is similar to EBT Gafchromic film. A high level of sensitivity is found for this film with a 1 cGy applied dose producing an approximate net optical density change of 0.3 at 636 nm. This high sensitivity combined with its relatively energy independent nature around the 100 kVp to 150 kVp x-ray energy range provides a unique enhancement in dosimetric measurement capabilities over currently available dosimetry films for CT applications.

  19. Determination of phytoplankton composition using absorption spectra.

    PubMed

    Martínez-Guijarro, R; Romero, I; Pachés, M; Del Río, J G; Martí, C M; Gil, G; Ferrer-Riquelme, A; Ferrer, J

    2009-05-15

    Characterisation of phytoplankton communities in aquatic ecosystems is a costly task in terms of time, material and human resources. The general objective of this paper is not to replace microscopic counts but to complement them, by fine-tuning a technique using absorption spectra measurements that reduces the above-mentioned costs. Therefore, the objective proposed in this paper is to assess the possibility of achieving a qualitative determination of phytoplankton communities by classes, and also a quantitative estimation of the number of phytoplankton cells within each of these classes, using spectrophotometric determination. Samples were taken in three areas of the Spanish Mediterranean coast. These areas correspond to estuary systems that are influenced by both continental waters and Mediterranean Sea waters. 139 Samples were taken in 7-8 stations per area, at different depths in each station. In each sample, the absorption spectrum and the phytoplankton classes (Bacyllariophyceae (diatoms), Cryptophyceae, Clorophyceae, Chrysophyceae, Prasynophyceae, Prymnesophyceae, Euglenophyceae, Cyanophyceae, Dynophyceae and the Synechococcus sp.) were determined. Data were analysed by means of the Partial Least Squares (PLS) multivariate statistical technique. The absorbances obtained between 400 and 750 nm were used as the independent variable and the cell/l of each phytoplankton class was used as the dependent variable, thereby obtaining models which relate the absorbance of the sample extract to the phytoplankton present in it. Good results were obtained for diatoms (Bacillarophyceae), Chlorophyceae and Cryptophyceae. PMID:19269434

  20. 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.

  1. X-Ray Absorption Spectra of Uranium by Synchrotron Radiation

    NASA Astrophysics Data System (ADS)

    Adachi, Hirohiko; Fujima, Kazumi; Taniguchi, Kazuo; Miyake, Chie; Imoto, Shosuke

    1981-08-01

    The X-ray absorption spectra of U, UO2 and UCl4 near the U OIV and OV thresholds have been measured by use of synchrotron radiation. The absorption peaks at about 100 eV and 110 eV are observed for all of these materials. However, the detailed structure of the spectra depend on the chemical state.

  2. Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

    NASA Astrophysics Data System (ADS)

    Coriani, Sonia; Koch, Henrik

    2015-11-01

    We present a simple scheme to compute X-ray absorption spectra (e.g., near-edge absorption fine structure) and core ionisation energies within coupled cluster linear response theory. The approach exploits the so-called core-valence separation to effectively reduce the excitation space to processes involving at least one core orbital, and it can be easily implemented within any pre-existing coupled cluster code for low energy states. We further develop a perturbation correction that incorporates the effect of the excluded part of the excitation space. The correction is shown to be highly accurate. Test results are presented for a set of molecular systems for which well converged results in full space could be generated at the coupled cluster singles and doubles level of theory only, but the scheme is straightforwardly generalizable to all members of the coupled cluster hierarchy of approximations, including CC3.

  3. Theoretical analysis of x-ray absorption spectra of Ti compounds used as catalysts in lithium amide/imide reactions

    NASA Astrophysics Data System (ADS)

    Tsumuraya, Takao; Shishidou, Tatsuya; Oguchi, Tamio

    2008-06-01

    We present a theoretical analysis and interpretation of the x-ray absorption near-edge structure of x-ray absorption spectroscopy (XAS) at the titanium K -edge of several Ti compounds for understanding catalysis mechanism in lithium amide LiNH2 and imide Li2NH systems for hydrogen storage. Our theoretical approach is based on first-principles calculations using all-electron full-potential linear augmented plane-wave method. Chemical bonding and local geometry of catalytically-active Ti states in the hydrogen desorption reaction LiNH2+LiH→Li2NH+H2 are investigated. It is found that XAS spectra of some compounds consisting of elements Li, N, H, and Ti are quite similar to measured ones of catalytically-active Ti compounds. We conclude that Ti ions may occupy the Li sites in LiNH2 during the reaction.

  4. Absorption Spectra of Magnesium Sulphite Hexahydrate Doped with Nickel

    NASA Astrophysics Data System (ADS)

    Petkova, Petya N.; Bunzarov, Zhelyu I.; Iliev, Ilia A.; Dimov, Todor N.

    2007-04-01

    In the work are presented absorption spectra of MgSO3.6H2O monocrystals doped with Ni. The spectra are measured in a wide spectral range (200 - 1200nm) at room temperature with polarized light. The impurity of Ni changes essentially the absorption of MgSO3.6H2O because it causes the appearance of additional spectral structures.

  5. 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.

  6. Effect of particle size and adsorbates on the L{sub 3}, L{sub 2} and L{sub 1} x-ray absorption near edge structure of supported Pt nanoparaticles.

    SciTech Connect

    Lei, Y.; Jelic, J.; Nitsche, L. C.; Meyer, R.; Miller, J.

    2011-04-01

    Pt nano-particles from about 1 to 10 nm have been prepared on silica, alkali-silica, alumina, silica-alumina, carbon and SBA-15 supports. EXAFS spectra of the reduced catalysts in He show a contraction of the Pt-Pt bond distance as particle size is decreased below 3 nm. The bond length decreased as much as 0.13 {angstrom} for 1 nm Pt particles. Adsorption of CO and H{sub 2} lead to a increase in Pt-Pt bond distance to that near Pt foil, e.g., 2.77 {angstrom}. In addition to changes in the Pt bond distance with size, as the particle size decreases below about 5 nm there is a shift in the XANES to higher energy at the L{sub 3} edge, a decrease in intensity near the edge and an increase in intensity beyond the edge. We suggest these features correspond to effects of coordination (the decrease at the edge) and lattice contraction (the increase beyond the edge). At the L{sub 2} edge, there are only small shifts to higher energy at the edge. However, beyond the edge, there are large increases in intensity with decreasing particle size. At the L{sub 1} edge there are no changes in position or shape of the XANES spectra. Adsorption of CO and H{sub 2} also lead to changes in the L{sub 3} and L{sub 2} edges, however, no changes are observed at the L1 edge. Density Functional Theory and XANES calculations show that the trends in the experimental XANES can be explained in terms of the states available near the edge. Both CO and H{sub 2} adsorption result in a depletion of states at the Fermi level but the creation of anti-bonding states above the Fermi level which give rise to intensity increases beyond the edge.

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

    NASA Technical Reports Server (NTRS)

    Niple, E. R.

    1979-01-01

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

  8. A comparison of fine structures in high-resolution x-ray-absorption spectra of various condensed organic molecules.

    PubMed

    Schoell, A; Zou, Y; Huebner, D; Urquhart, S G; Schmidt, Th; Fink, R; Umbach, E

    2005-07-22

    We report on a high-resolution C-K and O-K near-edge x-ray-absorption fine-structure (NEXAFS) study of large aromatic molecules in condensed thin films, namely, anhydrides 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride, 3,4,9,10-perylene-tetracarboxylic acid dianhydride, benzoperylene-(1,2)-dicarboxylic acid anhydride, and 1,8-naphthalene-dicarboxylic acid anhydride and the quinoic acenaphthenequinone. Due to the high-energy resolution of the third-generation synchrotron source BESSY II we observe large differences in the NEXAFS fine structures even for very similar molecules, resulting in a wealth of new information. The rich fine structure can unambiguously be assigned to the coupling of electronic transitions to vibronic excitations. Backed by ab initio calculations we present a detailed analysis of the spectra that allows the complete interpretation of the near-edge features. It also yields information on the vibronic properties in the electronically excited state as well as on the response of the electronic system upon core excitation. The strong differences in the electron-vibron coupling for different molecules are discussed. PMID:16095371

  9. Optical Absorption Spectra of Sodium Borate Cobalt Doped Glasses

    SciTech Connect

    Elokr, M. M.; Hassan, M. A.; Yaseen, A. M.; Elokr, R.

    2007-02-14

    Glassy system: xNa2O-(100-x-y)B2O3-yCo3O4 has been prepared by conventional melt quenching technique. Optical absorption spectra have been obtained in the range 300 - 2500 nm at room temperature. An absorption edge was observed in the near UV range, the analysis of which reveals that indirect transition is the dominant absorption mechanism. All prepared samples exhibit blue color, indicating that the Co ions are acted upon by tetrahedral ligand field. Obtained spectra were used to estimate some ligand field parameters.

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

    PubMed

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

    2016-01-15

    In this work, the terahertz (THz) absorption spectra of a set of nematic liquid crystals were studied using the density functional theories (DFT). An accurate assignment of the vibrational modes corresponding to absorption frequencies were performed using potential energy distribution (PED) in a frequency range of 0-3 THz. The impacts of different core structures on THz absorption spectra were discussed. The results indicate that scope of application must be considered in the LC-based THz device designing. This proposed work may give a useful suggestion on the design of novel liquid crystal material in THz wave. PMID:26476072

  11. C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach

    SciTech Connect

    Boccia, A.; Lanzilotto, V.; Marrani, A. G.; Zanoni, R.; Stranges, S.; Alagia, M.; Fronzoni, G.; Decleva, P.

    2012-04-07

    We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the {sigma}/{pi} hyperconjugation in EtFC and the {pi}-conjugation in VFC and EFC.

  12. C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach

    NASA Astrophysics Data System (ADS)

    Boccia, A.; Lanzilotto, V.; Marrani, A. G.; Stranges, S.; Zanoni, R.; Alagia, M.; Fronzoni, G.; Decleva, P.

    2012-04-01

    We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the σ/π hyperconjugation in EtFC and the π-conjugation in VFC and EFC.

  13. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

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

    SciTech Connect

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

    2013-05-15

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

  15. Probing molecular chirality by coherent optical absorption spectra

    SciTech Connect

    Jia, W. Z.; Wei, L. F.

    2011-11-15

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

  16. 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.

  17. Demonstrating Absorption Spectra Using Commercially Available Incandescent Light Bulbs

    NASA Astrophysics Data System (ADS)

    Birriel, Jennifer J.

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

  18. IR absorption spectra of cellulose obtained from ozonated wood

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  19. Substitution behavior of x(Na0.5K0.5)NbO3-(1 - x)BaTiO3 ceramics for multilayer ceramic capacitors by a near edge x-ray absorption fine structure analysis

    NASA Astrophysics Data System (ADS)

    Ha, Jooyeon; Ryu, Jiseung; Lee, Heesoo

    2014-06-01

    The doping effect of (Na0.5K0.5)NbO3 (NKN) as alternatives for rare-earth elements on the electrical properties of BaTiO3 has been investigated, in terms of their substitution behavior. The dielectric constant of a specimen with x = 0.05 was about 79% higher than that of pure BaTiO3, and the temperature coefficient of capacitance was satisfied by the X7R specification. The specimen with x = 0.05 showed the lowest tetragonality among the four compositions and had a fine grain size of <2 μm. Although the addition of NKN decreased the specimen's tetragonality, the electrical properties were enhanced by the formation of defect dipoles and conduction electrons, which resulted from an acceptor and donor substitution behavior. Through O K-edge near edge x-ray absorption fine structure spectroscopy, the practical substitution behavior was defined by the change in Ti 3d orbital states. The energy separation of the Ti 3d orbitals was more apparent with the specimen of x = 0.05, which is related to the donor level from the donor substitution of Nb5+ ion for Ti-sites. Therefore, the simultaneous substitution of Na+/K+ and Nb5+ ions into BaTiO3 can improve dielectric properties, based on the charge-transfer process.

  20. Theory and interpretation of L-shell X-ray absorption spectra

    NASA Astrophysics Data System (ADS)

    Nesvizhskii, Alexey I.

    X-ray absorption near edge structure (XANES) directly reflects the electronic structure in a material. However, despite significant progress in XANES theory, the quantitative analysis of XANES is not fully developed and remains a challenge. In this work, a detailed analysis of the L2,3 edge XANES in transition metals was performed using relativistic, self-consistent real space Green's function code FEFFS. Several prescriptions for taking into account core hole in calculations of x-ray absorption spectra (XAS) were discussed. It was found that in most cases of L2,3 edge XANES in transition metals, the initial state (ground state) calculations were in the best agreement with experimental data. A procedure was developed for quantitative applications of the sum rules for XAS, e.g., for x-ray magnetic circular dichroism and for obtaining hole counts. The approach is based on theoretical atomic calculations of transformations relating various experimental spectra to corresponding operator-spectral densities. This approach overcomes the difficulties of background subtraction and hole-count normalization of other sum rule analysis methods and yields quantitative values for spin- and orbital-moments from experimental absorption spectra. The developed approach was theoretically tested and applied to experimental XAS data in Cu, Ni, Co, Fe, and other materials. Hole counts obtained from XAS are often interpreted in terms of free-atom occupation numbers or Mulliken counts. We demonstrated that renormalized-atom (RA) counts are a better choice to characterize the configuration of occupied electron states in molecules and condensed matter. A projection-operator approach was introduced to subtract delocalized states and to determine such hole counts from XAS quantitatively. Theoretical tests for the s- and d-electrons in transition metals showed that the approach works well. A formalism was developed based on time dependent local density approximation (TDLDA) theory that takes

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

    ERIC Educational Resources Information Center

    Birriel, Jennifer J.

    2009-01-01

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

  2. The OH - absorption spectra of low doped lithium niobate crystals

    NASA Astrophysics Data System (ADS)

    Kong, Yongfa; Zhang, Wanlin; Xu, Jingjun; Yan, Wenbo; Liu, Hongde; Xie, Xiang; Li, Xiaochun; Shi, Lihong; Zhang, Guangyin

    2004-07-01

    The OH - absorption spectra of low doped lithium niobate (LiNbO 3) crystals have been investigated. Though no apparent band shift is observed in these absorption spectra, their shapes are quite different. In order to analyze the information on the defect structure underlying these OH - absorption bands, the normalization and difference methods were employed. It was found that although the doping concentrations are under the thresholds the doping ions have apparent affect to the site occupation of OH - ions. The OH - vibrations related to Mg Li+ (Mg 2+ occupying Li-site) and In Li2+ are 3483 and 3484 cm -1 in LiNbO 3:Mg and LiNbO 3:In crystals, respectively. The absorption peak of LiNbO 3:Ti (2.5 mol%) crystal at 3487 cm -1 is mainly related to Ti Li3+-OH - and the 3489 cm -1 peak of LiNbO 3:Mg (5.0 mol%), Ti (10.0 mol%) related to Mg Li+-OH -, Ti Nb--OH - and Ti Li3+-OH -. Doping with Na improves the peak intensity near 3466 cm -1 and induces a new absorption peak at 3470 cm -1. The absorption bands of LiNbO 3 crystals codoped with trivalent ions are associated with the co-effect of the doped ions and have some different characteristics from mono-doped crystals.

  3. Using X-ray absorption spectra to monitor specific radiation damage to anomalously scattering atoms in macromolecular crystallography.

    PubMed

    Oliéric, V; Ennifar, E; Meents, A; Fleurant, M; Besnard, C; Pattison, P; Schiltz, M; Schulze-Briese, C; Dumas, P

    2007-07-01

    Radiation damage in macromolecular crystals is not suppressed even at 90 K. This is particularly true for covalent bonds involving an anomalous scatterer (such as bromine) at the 'peak wavelength'. It is shown that a series of absorption spectra recorded on a brominated RNA faithfully monitor the extent of cleavage. The continuous spectral changes during irradiation preserve an 'isosbestic point', each spectrum being a linear combination of 'zero' and 'infinite' dose spectra. This easily yields a good estimate of the partial occupancy of bromine at any intermediate dose. The considerable effect on the near-edge features in the spectra of the crystal orientation versus the beam polarization has also been examined and found to be in good agreement with a previous study. Any significant influence of the (C-Br bond/beam polarization) angle on the cleavage kinetics of bromine was also searched for, but was not detected. These results will be useful for standard SAD/MAD experiments and for the emerging 'radiation-damage-induced phasing' method exploiting both the anomalous signal of an anomalous scatterer and the 'isomorphous' signal resulting from its cleavage. PMID:17582167

  4. Substitution behavior of x(Na{sub 0.5}K{sub 0.5})NbO{sub 3}-(1 − x)BaTiO{sub 3} ceramics for multilayer ceramic capacitors by a near edge x-ray absorption fine structure analysis

    SciTech Connect

    Ha, Jooyeon; Ryu, Jiseung; Lee, Heesoo

    2014-06-30

    The doping effect of (Na{sub 0.5}K{sub 0.5})NbO{sub 3} (NKN) as alternatives for rare-earth elements on the electrical properties of BaTiO{sub 3} has been investigated, in terms of their substitution behavior. The dielectric constant of a specimen with x = 0.05 was about 79% higher than that of pure BaTiO{sub 3}, and the temperature coefficient of capacitance was satisfied by the X7R specification. The specimen with x = 0.05 showed the lowest tetragonality among the four compositions and had a fine grain size of <2 μm. Although the addition of NKN decreased the specimen's tetragonality, the electrical properties were enhanced by the formation of defect dipoles and conduction electrons, which resulted from an acceptor and donor substitution behavior. Through O K-edge near edge x-ray absorption fine structure spectroscopy, the practical substitution behavior was defined by the change in Ti 3d orbital states. The energy separation of the Ti 3d orbitals was more apparent with the specimen of x = 0.05, which is related to the donor level from the donor substitution of Nb{sup 5+} ion for Ti-sites. Therefore, the simultaneous substitution of Na{sup +}/K{sup +} and Nb{sup 5+} ions into BaTiO{sub 3} can improve dielectric properties, based on the charge-transfer process.

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

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1988-10-01

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

  7. Theoretical investigations of absorption and fluorescence spectra of protonated pyrene.

    PubMed

    Chin, Chih-Hao; Lin, Sheng Hsien

    2016-05-25

    The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT). CASSCF calculations and absorption and emission spectra simulations by one-photon excitation equations were used to optimize the excited and ground state structures of protonated pyrene isomers. The absorption band was attributed to the S0 → S1 electronic transition in 1H-Py(+), and a band origin was used at 20580.96 cm(-1). The displaced harmonic oscillator approximation and Franck-Condon approximation were used to simulate the absorption spectrum of the (1) (1)A' ← X[combining tilde](1)A' transition of 1H-Py(+), and the main vibronic transitions were assigned for the first ππ* state. It shows that the vibronic structures were dominated by one of the eight active totally symmetric modes, with ν15 being the most crucial. This indicates that the electronic transition of the S1((1)A') state calculated in the adiabatic representation effectively includes a contribution from the adiabatic vibronic coupling through Franck-Condon factors perturbed by harmonic oscillators. The present method can adequately reproduce experimental absorption and fluorescence spectra of a gas phase. PMID:27181017

  8. Optical absorption spectra of palladium doped gold cluster cations

    SciTech Connect

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

    2015-01-21

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

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

    NASA Astrophysics Data System (ADS)

    Lobel, Alex

    2011-05-01

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

  10. Absorption Features in Spectra of Magnetized Neutron Stars

    SciTech Connect

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

    2011-09-21

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

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

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-10-01

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

  12. Optical Absorption Spectra of Hydrous Wadsleyite to 32 GPa

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  13. The x-ray absorption spectra of water and ice

    NASA Astrophysics Data System (ADS)

    Kong, Lingzhu; Wu, Xifan; Car, Roberto

    2012-02-01

    We calculate the x-ray absorption spectra of liquid water at STP, hexagonal ice and amorphous low- and high-density ice at T=269K, using the static Coulomb-hole and screened exchange self energy approach ootnotetextW. Chen, X. Wu and R. Car, PRL 105, 017802 (2008) . We take the nuclear quantum effects into account by averaging over the Feynman path-integral replicas. We find that quantum disorder is particularly important in liquid water where it substantially improves the structure ootnotetextJ. Morrone and R. Car, PRL 101, 017801 (2008) Compared to Ref. 2, we use an improved screening model that includes the approximate local field correction ootnotetextM. Hybertsen and S. G. Louie, PRB 37, 2733 (1988). The resulting spectra are in significantly better agreement with experiments than in previous calculations.

  14. Optical absorption and scattering spectra of pathological stomach tissues

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  15. NOTE: Visible absorption spectra of radiation exposed SIRAD dosimeters

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

    SIRAD badge dosimeters are a new type of personal dosimeter designed to measure radiation exposure up to 200 R and give a visual qualitative measurement of exposure. This is performed using the active dosimeter window, which contains a radiochromic material amalgamated in the badge assembly. When irradiated, the badges active window turns blue, which can be matched against the given colour chart for a qualitative assessment of the exposure received. Measurements have been performed to analyse the absorption spectra of the active window, and results show that the window automatically turns a blue colour upon irradiation and produces two peaks in the absorption spectra located at 617 nm and 567 nm. When analysed with a common computer desktop scanner, the optical density response of the film to radiation exposure is non-linear but reproducible. The net OD of the film was 0.21 at 50 R exposure and 0.31 at 200 R exposure when irradiated with a 6 MV x-ray energy beam. When compared to the calibration colour strips at 6 MV x-ray energy the film's OD response matches relatively well within 3.5%. An approximate 8% reduction in measured OD to exposure was seen for 250 kVp x-rays compared to 6 MV x-rays. The film provides an adequate measurement and visually qualitative assessment of radiation exposure for levels in the range of 0 to 200 R.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-05-01

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

  18. A Parallel Iterative Method for Computing Molecular Absorption Spectra.

    PubMed

    Koval, Peter; Foerster, Dietrich; Coulaud, Olivier

    2010-09-14

    We describe a fast parallel iterative method for computing molecular absorption spectra within TDDFT linear response and using the LCAO method. We use a local basis of "dominant products" to parametrize the space of orbital products that occur in the LCAO approach. In this basis, the dynamic polarizability is computed iteratively within an appropriate Krylov subspace. The iterative procedure uses a matrix-free GMRES method to determine the (interacting) density response. The resulting code is about 1 order of magnitude faster than our previous full-matrix method. This acceleration makes the speed of our TDDFT code comparable with codes based on Casida's equation. The implementation of our method uses hybrid MPI and OpenMP parallelization in which load balancing and memory access are optimized. To validate our approach and to establish benchmarks, we compute spectra of large molecules on various types of parallel machines. The methods developed here are fairly general, and we believe they will find useful applications in molecular physics/chemistry, even for problems that are beyond TDDFT, such as organic semiconductors, particularly in photovoltaics. PMID:26616067

  19. Constraining The Reionization History With QSO Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Gallerani, S.; Choudhury, T. R.; Ferrara, A.

    2006-08-01

    We use a semi-analytical approach to simulate absorption spectra of QSOs at high redshifts with the aim of constraining the cosmic reionization history. We consider two physically motivated and detailed reionization histories: (i) an Early Reionization Model (ERM) in which the intergalactic medium is reionized by PopIII stars at z~14, and (ii) a more standard Late Reionization Model (LRM) in which overlapping, induced by QSOs and normal galaxies, occurs at z~6. An example of simulated spectra is provided by FIG.1. From the analysis of current Lyα forest data at z<6, we conclude that it is impossible to disentangle the two scenarios, which fit equally well the observed Gunn-Peterson optical depth, flux probability distribution function and dark gap width distribution. At z>6, however, clear differences start to emerge which are best quantified by the dark gap width distribution. We find that 35 (zero) per cent of the lines of sight within 5.750Å in the rest frame of the QSO if re-ionization is not (is) complete at z>~6 (FIG.2). Similarly, the ERM predicts peaks of width ~1Å in 40 per cent of the lines of sight in the redshift range 6.0-6.6; in the same range, LRM predicts no peaks of width >0.8Å (FIG.3). We conclude that the dark gap and peak width statistics represent superb probes of cosmic reionization if about ten QSOs can be found at z>6.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  1. Molecular structures and absorption spectra assignment of corrole NH tautomers.

    PubMed

    Beenken, Wichard; Presselt, Martin; Ngo, Thien H; Dehaen, Wim; Maes, Wouter; Kruk, Mikalai

    2014-02-01

    The individual absorption spectra of the two NH tautomers of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole are assigned on the basis of the Gouterman four-orbital model and a quantum chemical TD-DFT study. The assignment indicates that the red-shifted T1 tautomer is the one with protonated pyrrole nitrogen atoms N(21), N(22) and N(23), whereas the blue-shifted T2 tautomer has pyrrole nitrogen atoms N(21), N(22) and N(24) protonated. A wave-like nonplanar distortion of the macrocycle in the ground state is found for both NH tautomers, with the wave axis going through the pyrroles containing N(22) and N(24). The 7C plane determined by the least-squares distances to the carbon atoms C1, C4, C5, C6, C9, C16, and C19 is suggested as a mean corrole macrocycle plane for the analysis of out-of-plane distortions. The magnitude of these distortions is distinctly different for the two NH tautomers, leading to substantial perturbations of their acid-base properties, which are rationalized by the interplay of the degree of out-of-plane distortion of the macrocycle as a whole and the tendency of the pyrrole nitrogen atoms toward pyramidalization, with the former leading to a basicity increase whereas the latter enhances the acidity. PMID:24432802

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

    USGS Publications Warehouse

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

    2014-01-01

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

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

    USGS Publications Warehouse

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

    2011-01-01

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

  4. X-ray Absorption Spectroscopy

    SciTech Connect

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

  5. Constraining the reionization history with QSO absorption spectra

    NASA Astrophysics Data System (ADS)

    Gallerani, S.; Choudhury, T. Roy; Ferrara, A.

    2006-08-01

    We use a semi-analytical approach to simulate absorption spectra of QSOs at high redshifts with the aim of constraining the cosmic reionization history. We consider two physically motivated and detailed reionization histories: (i) an early reionization model (ERM) in which the intergalactic medium is reionized by Pop III stars at z ~ 14, and (ii) a more standard late reionization model (LRM) in which overlapping, induced by QSOs and normal galaxies, occurs at z ~ 6. From the analysis of current Lyα forest data at z < 6, we conclude that it is impossible to disentangle the two scenarios, which fit equally well the observed Gunn-Peterson optical depth, flux probability distribution function and dark gap width distribution. At z > 6, however, clear differences start to emerge which are best quantified by the dark gap and peak width distributions. We find that 35 (0) per cent of the lines of sight (LOS) within 5.7 < z < 6.3 show dark gaps of widths >50Å in the rest frame of the QSO if reionization is not (is) complete at z >~ 6. Similarly, the ERM predicts peaks of width ~1Å in 40 per cent of the LOS in the redshift range 6.0-6.6 in the same range, LRM predicts no peaks of width >0.8Å. We conclude that the dark gap and peak width statistics represent superb probes of cosmic reionization if about ten QSOs can be found at z > 6. We finally discuss strengths and limitations of our method.

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

    PubMed

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

    2014-12-16

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

  7. Photon interference effect in x-ray absorption spectra over a wide energy range

    NASA Astrophysics Data System (ADS)

    Nishino, Y.; Ishikawa, T.; Suzuki, M.; Kawamura, N.; Kappen, P.; Korecki, P.; Haack, N.; Materlik, G.

    2002-09-01

    We consider fundamental structures in x-ray absorption spectra over a wide energy range. We formulate the elastic scattering in addition to the photoelectric absorption in recently reported photon interference x-ray absorption fine structure (πXAFS). The simulations show excellent agreement with experimental x-ray absorption spectra for platinum and tungsten powders far above and below the L absorption edges. πXAFS can be as big as in the order of 10% of XAFS, and cannot be easily neglected in detailed analysis of XAFS and related phenomena.

  8. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  9. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  10. Interpretation of NO2 absorption in twilight sky spectra

    NASA Astrophysics Data System (ADS)

    McMahon, B. B.

    1984-07-01

    A multiple scattering model has been developed to calculate nitrogen dioxide (NO2) absorption in the light from the zenith sky during twilight. Model studies show that this absorption is not very sensitive to the atmospheric temperature profile or to tropospheric NO2. The model was used to interpret some ground-based measurements of NO2 sky absorption. Values for the total stratospheric column amount vary from 2 to 12 x 10 to the 15th molec/sq cm, and the mean altitude of the stratospheric concentration profile is around 35 km. These observations are in broad agreement with those of other workers.

  11. Absorption spectra of graphene nanoribbons in a composite magnetic field

    NASA Astrophysics Data System (ADS)

    Li, T. S.; Wu, M. F.; Hsieh, C. T.

    2015-10-01

    The low-frequency optical absorption properties of graphene nanoribbons in a composite magnetic field are investigated by using the gradient approximation. The spectral function exhibits symmetric delta-function like prominent peaks structure in a uniform magnetic field, and changes to asymmetric square-root divergent peaks structure when subjecting to a composite field. These asymmetric divergent peaks can be further classified into principal and secondary peaks. The spectral intensity and frequency of the absorption peaks depend sensitively on the strength and modulation period of the composite field. The transition channels of the absorption peaks are also analyzed. There exists an optical selection rule which is caused by the orthogonal properties of the sublattice wave functions. The evolution of the spectral frequency of the absorption peaks with the field strength is explored.

  12. X-ray absorption spectra of graphene and graphene oxide by full-potential multiple scattering calculations with self-consistent charge density

    NASA Astrophysics Data System (ADS)

    Xu, Junqing; Krüger, Peter; Natoli, Calogero R.; Hayakawa, Kuniko; Wu, Ziyu; Hatada, Keisuke

    2015-09-01

    The x-ray absorption near-edge structure of graphene, graphene oxide, and diamond is studied by the recently developed real-space full potential multiple scattering (FPMS) theory with space-filling cells. It is shown how accurate potentials for FPMS can be generated from self-consistent charge densities obtained with other schemes, especially the projector augmented wave method. Compared to standard multiple scattering calculations in the muffin-tin approximation, FPMS gives much better agreement with experiment. The effects of various structural modifications on the graphene spectra are well reproduced. (1) Stacking of graphene layers increases the peak intensity in the higher energy region. (2) The spectrum of the C atom located at the edge of a graphene sheet shows a prominent pre-edge structure. (3) Adsorption of oxygen gives rise to the so-called interlayer-state peak. Moreover, O K-edge spectra of graphene oxide are calculated for three types of bonding, C-OH, C-O-C, and C-O, and the proportions of these bondings at 800 ∘C are deduced by fitting them to the experimental spectrum.

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

    NASA Astrophysics Data System (ADS)

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

    2002-04-01

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

  14. Effects of lowly ionized ions on silicon K-shell absorption spectra

    NASA Astrophysics Data System (ADS)

    Wei, H. G.; Shi, J. R.; Liang, G. Y.; Wang, F. L.; Zhong, J. Y.; Zhao, G.

    2016-05-01

    Context. In both astrophysical and laboratory plasmas, K-shell absorption spectra have become powerful diagnostic tools to investigate electron density and temperature. These spectra are also widely used to verify the opacity codes in laboratory settings. Aims: We report the effects of the low ionization silicon ions, namely from Si I to Si V, which have rarely been considered in previous models, on the K-shell silicon absorption spectra. Methods: The Si K-shell atomic data were calculated with the flexible atomic code, which is a fully relativistic atomic program with configuration interaction taken into consideration. Detailed level accounting models were employed to calculate the absorption spectra. Results: We calculate the Si absorption spectra in local thermodynamic equilibrium conditions with temperature and density ranges of 20-70 eV and ~1020 cm-3 to ~1022 cm-3, respectively, and show the contributions of the lowly ionized ions to the K-shell absorption spectra of silicon. We also investigate the effects of the different atomic data on the absorption spectra. We find good agreement between our results and these from OPLIB. Conclusions: We find that the contributions from these lowly ionized ions cannot be neglected at relative low temperatures. Accurate experimental measurements are needed to benchmark the theoretical calculations.

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

    NASA Astrophysics Data System (ADS)

    Grante, Ilze; Actins, Andris; Orola, Liana

    2014-08-01

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

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

    SciTech Connect

    Carnall, W.T.

    1985-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Hoepffner, Nicolas; Sathyendranath, Shubha

    1993-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  19. Vibronic Structures in Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous Solutions.

    PubMed

    Hiyama, Miyabi; Noguchi, Yoshifumi; Akiyama, Hidefumi; Yamada, Kenta; Koga, Nobuaki

    2015-01-01

    To elucidate the factors determining the spectral shapes and widths of the absorption and fluorescence spectra for keto and enol oxyluciferin and their conjugate bases in aqueous solutions, the intensities of vibronic transitions between their ground and first electronic excited states were calculated for the first time via estimation of the vibrational Franck-Condon factors. The major normal modes, overtones and combination tones in absorption and fluorescence spectra are similar for all species. The theoretical full widths at half maximum of absorption spectra are 0.4-0.7 eV and those for the fluorescence spectra are 0.4-0.5 eV, except for phenolate-keto that exhibits exceptionally sharp peak widths due to the dominance of the 0-0' or 0'-0 band. These spectral shapes and widths explain many relevant features of the experimentally observed spectra. PMID:25946599

  20. Infrared absorption spectra of methylidene radicals in solid neon.

    PubMed

    Lu, Hsiao-Chi; Lo, Jen-Iu; Lin, Meng-Yeh; Peng, Yu-Chain; Chou, Sheng-Lung; Cheng, Bing-Ming; Ogilvie, J F

    2014-07-28

    Infrared absorption lines of methylidene--(12)C(1)H, (13)C(1)H, and (12)C(2)H--dispersed in solid neon at 3 K, recorded after photolysis of methane precursors with vacuum-ultraviolet light at 121.6 nm, serve as signatures of these trapped radicals. PMID:24912563

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    USGS Publications Warehouse

    Feinstein, H.I.

    1956-01-01

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

  3. Data processing of absorption spectra from photoionized plasma experiments at Za)

    NASA Astrophysics Data System (ADS)

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.

    2010-10-01

    We discuss the processing of x-ray absorption spectra from photoionized plasma experiments at Z. The data was recorded with an imaging spectrometer equipped with two elliptically bent potassium acid phthalate (KAP) crystals. Both time-integrated and time-resolved data were recorded. In both cases, the goal is to obtain the transmission spectra for quantitative analysis of plasma conditions.

  4. Determining neutrino absorption spectra at ultra-high energies

    SciTech Connect

    Scholten, O; Van Vliet, A R E-mail: A.R.van.Vliet@student.rug.nl

    2008-06-15

    A very efficient method for measuring the flux of ultra-high energy (UHE) neutrinos is through the detection of radio waves which are emitted by the particle shower in the lunar regolith. The highest acceptance is reached for radio waves in the frequency band of 100-200 MHz which can be measured with modern radio telescopes. In this work we investigate the sensitivity of this detection method to structures in the UHE neutrino spectrum caused by their absorption on the low energy relic anti-neutrino background through the Z boson resonance. The position of the absorption peak is sensitive to the neutrino mass and the redshift of the source. A new generation of low frequency digital radio telescopes will provide excellent detection capabilities for measuring these radio pulses, thus making our consideration here very timely.

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

    NASA Technical Reports Server (NTRS)

    Liang, Edison P.; Kargatis, Vincent E.

    1994-01-01

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

  6. Electronic absorption spectra of some arylidene pyrazolone derivatives

    NASA Astrophysics Data System (ADS)

    Mahmoud, M. R.; El-Kashef, H. S.; El-Hamide, R. Abd

    The u.v. and visible spectra of some 1 - phenyl - 3 - methyl - 4 - arylidene - 2 - pyrazolin - 5 - one derivatives are investigated in pure and mixed organic solvents as well as in aqueous buffer solutions. Electronic transitions have been identified as either locally excited or predominantly charge transfer states. Moreover, the spectra of the hydroxy derivatives in proton acceptor solvents (DMF, DMSO, ethanol) are characterized by an extra band located at longer wavelengths, which is ascribed to an intermolecular CT transition. This involves an electron transfer from the lone pair of electrons of the oxygen atom of the solvent molecules (ψ ol) to the antibonding orbital of the substituent OH group. The spectral shifts are discussed in terms of medium effects and in relation to molecular structure. The variation of absorbance with pH is utilized for the determination of p K a for the dimethylamino and hydroxy derivatives.

  7. Infrared absorption spectra of human malignant tumor tissues

    NASA Astrophysics Data System (ADS)

    Skornyakov, I. V.; Tolstorozhev, G. B.; Butra, V. A.

    2008-05-01

    We used infrared spectroscopy methods to study the molecular structure of tissues from human organs removed during surgery. The IR spectra of the surgical material from breast, thyroid, and lung are compared with data from histological examination. We show that in malignant neoplasms, a change occurs in the hydrogen bonds of protein macromolecules found in the tissue of the studied organs. We identify the spectral signs of malignant pathology.

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

  10. Polarized absorption spectra of (2,2) carbon nanotubes aligned in channels of an AEL crystal

    NASA Astrophysics Data System (ADS)

    Chen, Yanping; Zhai, Jianpang; Li, Irene Ling; Ruan, Shuangchen; Tang, Zikang

    2015-11-01

    We report polarized absorption spectra for the (2,2) tubes arrayed in the one-dimensional channels of an AlPO4-11 (AEL) single crystal. Strong polarization dependence is observed indicating a preferential optical dipole along the axis of carbon nanotubes. By correlating with the absorption spectra and First-principles local density function (LDA) calculation, the absorption peak at 2.95 eV is uniquely assigned to semiconducting type (2,2) tubes, and peaks at 2.67 and 2.40 eV are corresponding to metallic type (2,2) tubes.

  11. Infrared absorption spectra of pure and doped YAl3(BO3)4 single crystals

    NASA Astrophysics Data System (ADS)

    Kovács, L.; Mazzera, M.; Beregi, E.; Capelletti, R.

    2009-02-01

    Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl3(BO3)4 single crystals in the 3350- 3650 cm-1 wave number region. Two of them, peaking at about 3377 cm-1 and 3580 cm-1 in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH- ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm-1 at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.

  12. Influence of electric fields on absorption spectra of AAB-stacked trilayer graphene

    NASA Astrophysics Data System (ADS)

    Chiu, Chih-Wei; Chen, Rong-Bin

    2016-06-01

    The tight-binding model and gradient approximation are, respectively, used to calculate the band structures and the absorption spectra of AAB-stacked trilayer graphene (AAB-TLG). AAB stacking, the lowest symmetric geometric structure in trilayer systems, induces the most atomic interactions, and thus, complicates the energy dispersions and the joint density of states. AAB stacking enriches the optical absorption spectra [A(ω)], which dictate the characteristics of the electronic structure. A(ω) are changed by the static electric field, such as the intensity, frequency, and number of absorption structures. These results contrast sharply with those for TLG in other stacking configurations.

  13. Artifacts in Absorption Measurements of Organometal Halide Perovskite Materials: What Are the Real Spectra?

    PubMed

    Tian, Yuxi; Scheblykin, Ivan G

    2015-09-01

    Organometal halide (OMH) perovskites have attracted lots of attention over the last several years due to their very promising performance as the materials for solar cells and light-emitting devices. Photophysical processes in these hybrid organic-inorganic semiconductors are still heavily debated. To know precise absorption spectra is absolutely necessary for quantitative understanding of the fundamental properties of OMH perovskites. We show that to measure the absorption of perovskite materials correctly is a difficult task which could be easily overlooked by the community. Many of the published absorption spectra exhibit a characteristic step-like featureless shape due to light scattering, high optical density of individual perovskite crystals and poor coverage of the substrate. We show how to recognize these artifacts, to avoid them, and to use absorption spectra of films for estimation of the surface coverage ratio. PMID:27120683

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

    SciTech Connect

    Weger, H.T.; Reed, D.

    1996-02-01

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

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

    SciTech Connect

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

    2014-09-01

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

  16. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  17. Electron energy-loss near-edge structures of 3d transition metal oxides recorded at high-energy resolution.

    PubMed

    Mitterbauer, C; Kothleitner, G; Grogger, W; Zandbergen, H; Freitag, B; Tiemeijer, P; Hofer, F

    2003-09-01

    Near-edge fine structures of the metal L(2,3) and O K-edges in transition metal-oxides have been studied with a transmission electron microscope equipped with a monochromator and a high-resolution imaging filter. This system enables the recording of EELS spectra with an energy resolution of 0.1eV thus providing new near-edge fine structure details which could not be observed previously by EELS in conventional TEM instruments. EELS-spectra from well-defined oxides like titanium oxide (TiO(2)), vanadium oxide (V(2)O(5)), chromium oxide (Cr(2)O(3)), iron oxide (Fe(2)O(3)), cobalt oxide (CoO) and nickel oxide (NiO) have been measured with the new system. These spectra are compared with EELS data obtained from a conventional microscope and the main spectral features are interpreted. Additionally, the use of monochromised TEMs is discussed in view of the natural line widths of K and L(2,3) edges. PMID:12871809

  18. Influence of laser radiation on induced absorption spectra of pure quartz glass optical fibers

    NASA Astrophysics Data System (ADS)

    Dianov, Y. M.; Karpechev, V. N.; Korniyenko, L. S.; Rybaltovskiy, A. O.; Chernov, P. V.

    1986-01-01

    The influence of laser radiation on radiation color centers and their associated induced absorption in the spectra of irradiated glass optical fibers is investigated. The glass fiber specimens employed had 40 to 50 micron diameter cores made of day pure quartz glass. The optical fibers were 6 to 20 meters long, produced by chemical precipitation from the gaseous phase and clad with reflecting borosilicate glass. Spectral measurements of the induced absorption in the ultraviolet region were made using an FEU-71 photodetector and a sounding radiation source. The stimulated laser emission power in the cross section of the optical fiber was measured by a photodiode; the absorption spectra were recorded by the fragment method. Eight different types of color centers were isolated whose bands cover practically the entire observed absorption spectra. The connection found between color centers and a 340 nm absorption band, and color center with absorption in the infrared band, indicate that absorption in the ultraviolet band can have a significant influence on the amount of induced absorption in the infrared band.

  19. Linewidths in excitonic absorption spectra of cuprous oxide

    NASA Astrophysics Data System (ADS)

    Schweiner, Frank; Main, Jörg; Wunner, Günter

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    We have monitored 12 intrinsic narrow absorption lines (NALs) in five quasars and seven mini-broad absorption lines (mini-BALs) in six quasars for a period of 4-12 yr (1-3.5 yr in the quasar rest-frame). We present the observational data and the conclusions that follow immediately from them, as a prelude to a more detailed analysis. We found clear variability in the equivalent widths (EWs) of the mini-BAL systems but no easily discernible changes in their profiles. We did not detect any variability in the NAL systems or in narrow components that are often located at the center of mini-BAL profiles. Variations in mini-BAL EWs are larger at longer time intervals, reminiscent of the trend seen in variable BALs. If we assume that the observed variations result from changes in the ionization state of the mini-BAL gas, we infer lower limits to the gas density ~103-105 cm-3 and upper limits on the distance of the absorbers from the central engine of the order of a few kiloparsecs. Motivated by the observed variability properties, we suggest that mini-BALs can vary because of fluctuations of the ionizing continuum or changes in partial coverage while NALs can vary primarily because of changes in partial coverage. Based on data collected at Subaru telescope, which is operated by the National Astronomical Observatory of Japan. Based on observations obtained at the European Southern Observatory at La Silla, Chile in programs 65.O-0063(B), 65.O-0474(A), 67.A-0078(A), 68.A-0461(A), 69.A-0204(A), 70.B-0522(A), 072.A-0346(A), 076.A-0860(A), 079.B-0469(A), and 166.A-0106(A).

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed

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

    2015-01-01

    Infrared spectroscopy is a powerful tool in protein science due to its sensitivity to changes in secondary structure or conformation. In order to take advantage of the full power of infrared spectroscopy in structural studies of proteins, complex band contours, such as the amide I band, have to be decomposed into their main component bands, a process referred to as curve fitting. In this paper, we report on an improved curve fitting approach in which absorption spectra and second derivative spectra are fitted simultaneously. Our approach, which we name co-fitting, leads to a more reliable modelling of the experimental data because it uses more spectral information than the standard approach of fitting only the absorption spectrum. It also avoids that the fitting routine becomes trapped in local minima. We have tested the proposed approach using infrared absorption spectra of three mixed α/β proteins with different degrees of spectral overlap in the amide I region: ribonuclease A, pyruvate kinase, and aconitase. PMID:26184143

  3. Absorption spectra of typical space materials in the vacuum ultraviolet

    NASA Astrophysics Data System (ADS)

    Muscari, J. A.

    1981-01-01

    In order to develop a data base for potential optical degradation of space vacuum ultraviolet instruments, the collected volatile condensed material (CVCM) transmittance was measured in the wavelength region from 115 nm to 300 nm. The parent outgassing materials included: the adhesives, Ablebond 36-2, Trabond BB-2116, EA-9309, and Scotchweld 2216; the paints, Chemglaze Z-306, Z-306 over 9922 primer, Z-306 over AP-131 primer, Cat-A-Lac 463-3-8, 463-3-8 over primer, 3M Nextel 401-C10, and 401-C10 over 901-P1 primer; the resins, Fiberite 934, Solithane 113/C113-300 Formulation no. 1, and 113/C113-300 Formulation no. 8; the lubricants, Lube-Lok 4306 and RT/Duroid 5813; and the double-sided adhesive tape 3M-415. The effect of thermal vacuum conditioning of selected materials was also studied. The transmittance measurements were used to calculate the absorption coefficient for each of 28 different source materials versus wavelength.

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

    NASA Astrophysics Data System (ADS)

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

    2001-10-01

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

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

    PubMed

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

    2010-01-01

    A non-destructive and novel in situ acoustic sensor approach based on the sound absorption spectra was developed for identifying and classifying different seed types. The absorption coefficient spectra were determined by using the impedance tube measurement method. Subsequently, a multivariate statistical analysis, i.e., principal component analysis (PCA), was performed as a way to generate a classification of the seeds based on the soft independent modelling of class analogy (SIMCA) method. The results show that the sound absorption coefficient spectra of different seed types present characteristic patterns which are highly dependent on seed size and shape. In general, seed particle size and sphericity were inversely related with the absorption coefficient. PCA presented reliable grouping capabilities within the diverse seed types, since the 95% of the total spectral variance was described by the first two principal components. Furthermore, the SIMCA classification model based on the absorption spectra achieved optimal results as 100% of the evaluation samples were correctly classified. This study contains the initial structuring of an innovative method that will present new possibilities in agriculture and industry for classifying and determining physical properties of seeds and other materials. PMID:22163455

  6. A Novel Acoustic Sensor Approach to Classify Seeds Based on Sound Absorption Spectra

    PubMed Central

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

    2010-01-01

    A non-destructive and novel in situ acoustic sensor approach based on the sound absorption spectra was developed for identifying and classifying different seed types. The absorption coefficient spectra were determined by using the impedance tube measurement method. Subsequently, a multivariate statistical analysis, i.e., principal component analysis (PCA), was performed as a way to generate a classification of the seeds based on the soft independent modelling of class analogy (SIMCA) method. The results show that the sound absorption coefficient spectra of different seed types present characteristic patterns which are highly dependent on seed size and shape. In general, seed particle size and sphericity were inversely related with the absorption coefficient. PCA presented reliable grouping capabilities within the diverse seed types, since the 95% of the total spectral variance was described by the first two principal components. Furthermore, the SIMCA classification model based on the absorption spectra achieved optimal results as 100% of the evaluation samples were correctly classified. This study contains the initial structuring of an innovative method that will present new possibilities in agriculture and industry for classifying and determining physical properties of seeds and other materials. PMID:22163455

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

    PubMed

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

    2016-06-29

    A generalized tight-binding model is developed to investigate the feature-rich magneto-optical properties of AAB-stacked trilayer graphene. Three intragroup and six intergroup inter-Landau-level (inter-LL) optical excitations largely enrich magneto-absorption peaks. In general, the former are much higher than the latter, depending on the phases and amplitudes of LL wavefunctions. The absorption spectra exhibit single- or twin-peak structures which are determined by quantum modes, LL energy spectra and Fermion distribution. The splitting LLs, with different localization centers (2/6 and 4/6 positions in a unit cell), can generate very distinct absorption spectra. There exist extra single peaks because of LL anti-crossings. AAB, AAA, ABA, and ABC stackings considerably differ from one another in terms of the inter-LL category, frequency, intensity, and structure of absorption peaks. The main characteristics of LL wavefunctions and energy spectra and the Fermi-Dirac function are responsible for the configuration-enriched magneto-optical spectra. PMID:27305856

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

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  10. 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.

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

    ERIC Educational Resources Information Center

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

    2004-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Roesler, Collin S.; Pery, Mary Jane

    1995-01-01

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

  13. 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.

  14. Absorption Spectra and Absorption Coefficients for Methane in the 750-940 nm region obtained by Intracavity Laser Spectroscopy

    NASA Astrophysics Data System (ADS)

    O'Brien, J. J.; Cao, H.

    2000-10-01

    Methane spectral features are prominent in the reflected sunlight spectra from the outer planets and some of their major satellites and can provide useful information on the atmospheres of those bodies. Methane bands occurring in the visible to near-IR region are particularly important because for many of these planetary bodies, methane bands occurring in the IR are saturated. Spectral observations of these bodies also are being made at increasingly higher resolution. In order to interpret the planetary spectra, laboratory data for methane obtained at appropriate sample conditions and spectral resolution are required. Since the visible to near-IR spectrum of methane is intrinsically weak, sensitive techniques are required to perform the laboratory measurements. We have employed the intracavity laser spectroscopy (ILS) technique to record methane spectrum in the visible to near-IR region. New results for room temperature methane in the 10,635 - 13,300 cm-1 region and for liquid nitrogen temperature (77 K) methane in the 10,860 - 11,605 cm-1 region will be presented. Spectra throughout the more strongly absorbing sections will be shown. These spectra are acquired at a resolution of 400,000 - 500,000 and are calibrated using iodine reference spectra acquired from an extra-cavity cell at nearly the same time as when the methane data are recorded. From the spectra, absorption coefficients are determined and these are presented as averages over 1 Å and 1 cm-1 intervals. In order to obtain the results, spectra are deconvolved for the instrument function using a Fourier transform technique. The validity of the approach is verified from studies of isolated oxygen lines in the A band occurring around 760 nm. Good agreement is observed between the intensity values determined from the FT deconvolution and integration method and those derived by fitting the observed line profiles to Voigt line-shapes convoluted with the instrument function. The methane results are compared

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

    NASA Technical Reports Server (NTRS)

    Beltrametti, M.

    1980-01-01

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

  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. Theoretical collision-induced rototranslational absorption spectra for the outer planets - H2-CH4 pairs

    NASA Astrophysics Data System (ADS)

    Borysow, A.; Frommhold, L.

    1986-05-01

    Computations of the rototranslational absorption spectra of H2-CH4 molecular complexes are presented which are based on the classical multipole expansion; spectral profiles are obtained from an exact quantum formalism. The interaction potential is based on laboratory measurements of H2-CH4 pairs at 195 and 297K. The computed spectra provide the most reliable temperature dependence of the absorption coefficient as a function of frequency that can be made under the present circumstances. A theoretical description of the H2CH4 dimer features is given in the isotropic potential approximation. This work is significant for the modeling of the far-infrared absorption of the outer planets' atmospheres, where H2 and CH4 are present.

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

    SciTech Connect

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

    2012-07-15

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

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

    PubMed

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

    2012-07-01

    We report here the calibration and analysis techniques used to obtain spatially resolved density and temperature measurements of a pair of imploding aluminum wires from x-ray absorption spectra. A step wedge is used to measure backlighter fluence at the film, allowing transmission through the sample to be measured with an accuracy of ±14% or better. A genetic algorithm is used to search the allowed plasma parameter space and fit synthetic spectra with 20 μm spatial resolution to the measured spectra, taking into account that the object plasma nonuniformity must be physically reasonable. The inferred plasma conditions must be allowed to vary along the absorption path in order to obtain a fit to the spectral data. The temperature is estimated to be accurate to within ±25% and the density to within a factor of two. This information is used to construct two-dimensional maps of the density and temperature of the object plasma. PMID:22852690

  20. Calculation of the Kramers-Kronig transform of X-ray spectra by a piecewise Laurent polynomial method.

    PubMed

    Watts, Benjamin

    2014-09-22

    An algorithm is presented for the calculation of the Kramers-Kronig transform of a spectrum via a piecewise Laurent polynomial method. This algorithm is demonstrated to be highly accurate, while also being computationally efficient. The algorithm places no requirements on data point spacing and is capable of integrating across the full spectrum (i.e. from zero to infinity). Further, we present a computer application designed to aid in calculating the Kramers-Kronig transform on near-edge experimental X-ray absorption spectra (extended with atomic scattering factor data) in order to produce the dispersive part of the X-ray refractive index, including near-edge features. PMID:25321829

  1. Theoretical calculations of X-ray absorption spectra of a copper mixed ligand complex using computer code FEFF9

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Shrivastava, B. D.

    2014-09-01

    The terms X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) refer, respectively, to the structure in the X-ray absorption spectrum at low and high energies relative to the absorption edge. Routine analysis of EXAFS experiments generally makes use of simplified models and several many-body parameters, e.g. mean free paths, many-body amplitude factors, and Debye-Waller factors, as incorporated in EXAFS analysis software packages like IFEFFIT which includes Artemis. Similar considerations apply to XANES, where the agreement between theory and experiment is often less satisfactory. The recently available computer code FEFF9 uses the real-space Green's function (RSGF) approach to calculate dielectric response over a broad spectrum including the dominant low-energy region. This code includes improved treatments of many-body effects such as inelastic losses, core-hole effects, vibrational amplitudes, and the extension to full spectrum calculations of optical constants including solid state effects. In the present work, using FEFF9, we have calculated the X-ray absorption spectrum at the K-edge of copper in a complex, viz., aqua (diethylenetriamine) (isonicotinato) copper(II), the crystal structure of which is unknown. The theoretical spectrum has been compared with the experimental spectrum, recorded by us at the XAFS beamline 11.1 at ELETTRA synchrotron source, Italy, in both XANES and EXAFS regions.

  2. Communication: On the difficulty of reproducibly measuring PbCl2 X-ray absorption spectra

    NASA Astrophysics Data System (ADS)

    Schwartz, Craig P.; Prendergast, David

    2015-09-01

    Previous measurements of the X-ray absorption spectra of PbCl2 at the chlorine K-edge have shown significant variation between different studies. Herein, using first principles simulations of X-ray absorption spectroscopy, we show that the observed spectral variations are due to the generation of Cl2 gas and depletion of chlorine from PbCl2, consistent with what is observed during ultraviolet absorption for the same compound. We note that Cl2 gas generation can also be initiated using higher resonant X-ray energies, including Pb X-ray absorption edges. While this casts doubt on previous interpretations of certain measurements, it does indicate a means of generating chlorine gas during in situ experiments by passing high energy x-rays through a hard x-ray transparent medium and onto PbCl2.

  3. Communication: On the difficulty of reproducibly measuring PbCl2 X-ray absorption spectra.

    PubMed

    Schwartz, Craig P; Prendergast, David

    2015-09-21

    Previous measurements of the X-ray absorption spectra of PbCl2 at the chlorine K-edge have shown significant variation between different studies. Herein, using first principles simulations of X-ray absorption spectroscopy, we show that the observed spectral variations are due to the generation of Cl2 gas and depletion of chlorine from PbCl2, consistent with what is observed during ultraviolet absorption for the same compound. We note that Cl2 gas generation can also be initiated using higher resonant X-ray energies, including Pb X-ray absorption edges. While this casts doubt on previous interpretations of certain measurements, it does indicate a means of generating chlorine gas during in situ experiments by passing high energy x-rays through a hard x-ray transparent medium and onto PbCl2. PMID:26395677

  4. IR absorption and Raman spectra of single crystals of stable germanium isotopes

    NASA Astrophysics Data System (ADS)

    Gavva, V. A.; Kotereva, T. V.; Lipskiy, V. A.; Nezhdanov, A. V.

    2016-02-01

    The Raman and IR absorption spectra of single crystals of germanium isotopes 72Ge, 73Ge, 74Ge, and 76Ge in the region of phonon absorption and interband electronic transitions are studied at room temperature. The dependence of the Raman peak position on the atomic mass has the form ν ~ M -1/2. The shifts of the phonon absorption peaks of individual isotopes with respect to germanium of natural isotopic composition natGe are determined. With increasing average atomic mass of germanium, these peaks shift to longer wavelengths. In the region of interband electronic transitions, the intrinsic absorption edge of 76Ge is observed to shift by 1 meV to higher energies with respect to Ge of natural isotopic composition. For isotopes with atomic masses close to that of natural germanium (72Ge,73Ge, 74Ge), we found no significant difference in the band gap width at room temperature.

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

    SciTech Connect

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

    2013-11-15

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

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

    PubMed

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

    2016-05-10

    The absorption spectra of exhaust gases (H2O, CO, CO2, NO, NO2, and SO2) and aerosol (soot and Al2O3) particles were modeled at different temperatures for the first time and suitable spectral ranges were determined for conducting laser remote sensing of the combustion products of jet engines. The calculations were conducted on the basis of experimental concentrations of the substances and the sizes of the aerosol particles. The temperature and geometric parameters of jet engine exhausts were also taken from the literature. The absorption spectra were obtained via the line-by-line method, making use of the spectral line parameters from the authors' own high-temperature databases (for NO2 and SO2 gases) and the HITEMP 2010 database, and taking into account atmospheric transmission. Finally, the theoretical absorption spectra of the exhaust gases were plotted at temperatures of 400, 700, and 1000 K, and the impact of aerosol particles on the total exhaust spectra was estimated in spectral ranges suitable for remote sensing applications. PMID:27168298

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

    NASA Astrophysics Data System (ADS)

    Kokaly, Raymond F.; Skidmore, Andrew K.

    2015-12-01

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

  8. Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

    NASA Astrophysics Data System (ADS)

    Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

    2007-12-01

    Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

  10. Studies on external electric field effects on absorption and fluorescence spectra of NADH

    NASA Astrophysics Data System (ADS)

    Nakabayashi, Takakazu; Islam, Md. Serajul; Li, Liming; Yasuda, Masahide; Ohta, Nobuhiro

    2014-03-01

    Electric field effects on absorption and fluorescence spectra have been investigated for NADH that is a representative autofluorescent chromophore in cells. The change in electric dipole moment following absorption is significant in the electroabsorption spectrum, indicating charge transfer character in the excited state. The fluorescence intensity decreases in the presence of an electric field, which arises from the field-induced increase in the rate of the non-radiative process. The blue shift of the fluorescence spectrum and the increase in the fluorescence lifetime of NADH are measured in yeast cells, which is discussed in terms of a local electric field around NADH.

  11. Absorption spectra of monolayer MoS2 in high magnetic field

    NASA Astrophysics Data System (ADS)

    Yang, Hung-Duen; Her, Jim-Long; Takeyama, Shojiro; Matsuda, Yasuhiro; Wang, Kai-Hsuan

    2015-03-01

    We have measured the absorption spectra of monolayer MoS2 film at several temperatures in pulsed high magnetic fields up to 52 T. At room temperature, the observed spectrum dominated by two main peaks, which are located at 660 nm and 606 nm. These peaks are ascribed to excition and trion absorption peaks respectively [1]. At low temperature (4.2 K), two peaks show the blue shift to 633 nm and 588 nm, respectively. Irrespective of the temperature, applying magnetic field does not show pronounced influence on the peaks even in 52 T.

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

    NASA Technical Reports Server (NTRS)

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

    1974-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Du, Ping

    1993-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  16. Impact of different visible light spectra on oxygen absorption and surface discoloration of bologna sausage.

    PubMed

    Böhner, Nadine; Rieblinger, Klaus

    2016-11-01

    The objective of this study was to evaluate the influence of several visible light spectra in various intensities on the oxygen absorption and surface color of sliced bologna. Sausage samples were stored in a gastight model packaging system and illuminated at 5°C with six single-colored LEDs covering the main part of the visible light spectrum. The initial oxygen level was set at 0.5% in order to simulate common residual oxygen amounts in conventional packaging. The oxygen absorption and the discoloration measured as changes in CIE a*-value were dependent from the applied light intensity. The color stability of bologna was differently affected by light of various wavelengths. The results show that the use of suitable LEDs with specific spectra for display illumination can help to reduce the light induced deterioration of cured sausages in retail markets. PMID:27343458

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Absorption features in the 3 micron spectra of highly obscured objects

    NASA Technical Reports Server (NTRS)

    Smith, Robert G.; Sellgren, Kris; Tokunaga, Alan T.

    1989-01-01

    Using the IRTF cooled-grating spectrometer moderate resolution 2.4 to 3.8 micron spectra of a selection of IR protostars and one object located behind the Taurus dark cloud were obtained. Two examples of the spectra are presented. It is clear that the absorption near 3.07 micron is dominated by H2O ice and a comparison between the spectra and a simple H2O ice model allows a temperature estimate for the hottest ice-coated grains in these sources. Higher resolution observations showed no indication of the absorption due to the N-H stretching vibration of NH3 near 2.963 micron. The most plausible explanation for the 3.3 and 3.45 micron features appears to be absorption by the mixture of hydrocarbons, although they cannot be identified with features already attributed to hydrocarbons in the ISM, reflection nebulae and Comets. However these features appear the same for all sources in the sample, including Elias 16, thus implying a very similar mixture of molecules in each source.

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

    PubMed

    Chandran, Satheesh; Varma, Ravi

    2016-01-15

    1, 4-Dioxane (DX) is a commonly found ether in industrially polluted atmosphere. The near infrared absorption spectra of this compound has been recorded in the region 5900-8230 cm(-1) with a resolution of 0.08 cm(-1) using a novel Fourier transform incoherent broadband cavity-enhanced absorption spectrometer (FT-IBBCEAS). All recorded spectra were found to contain regions that are only weakly perturbed. The possible combinations of fundamental modes and their overtone bands corresponding to selected regions in the measured spectra are tabulated. Two interesting spectral regions were identified as 5900-6400 cm(-1) and 8100-8230 cm(-1). No significant spectral interference due to presence of water vapor was observed suggesting the suitability of these spectral signatures for spectroscopic in situ detection of DX. The technique employed here is much more sensitive than standard Fourier transform spectrometer measurements on account of long effective path length achieved. Hence significant enhancement of weaker absorption lines above the noise level was observed as demonstrated by comparison with an available measurement from database. PMID:26474242

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Chandran, Satheesh; Varma, Ravi

    2016-01-01

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

  2. UV Absorption and Luminescence Spectra of [2.2]Paracyclophane Phenyl Derivatives

    NASA Astrophysics Data System (ADS)

    Nurmukhametov, R. N.; Shapovalov, A. V.; Antonov, D. Yu.

    2016-03-01

    UV absorption, fluorescence emission and excitation, and fluorescence excitation synchronous scanning spectra at 298 K and fluorescence and phosphorescence spectra at 77 K were measured for solutions of 4-phenyl- ( I) and 4,12-( II), 4,15- ( III), and 4,16-diphenyl derivatives ( IV) of [2.2]paracyclophane. Analysis of absorption spectra shows that they are determined by two types of chromophores (biphenyl and paracyclophane). It was shown that their weak long wavelength band (310-340 nm) and fluorescence band are governed by the same electron transition from the ground to an excimer-like excited state, as in the case of the unsubstituted macrocycle. Phenyl substitution shows only a weak influence on the energy of this transition. Strong absorption bands of I- IV at 230-310 nm originate from electronic transitions of biphenyl groups in these molecules. The strong bands of isomeric II- IV (with two biphenyl chromophores) differ significantly. It was supposed that this phenomenon was caused by different resonance interaction between electron oscillators (transitions) of the two biphenyl chromophores leading to different splitting of their excited states.

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

    PubMed

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

    2011-11-01

    Protochlorophyllide (Pchlide) is a natural porphyrin, a precursor of chlorophyll, synthesized by plants for its photosynthetic apparatus. The pigment spontaneously forms aggregates when dissolved in neat water solution. We present here calculations of the transient absorption spectra and its comprising components (ground-state bleach, stimulated emission, and excited-state absorption) for a strongly excitonically coupled linear chain of four Pchlide chromophores, using exciton theory with phenomenological Gaussian line shapes and without energetic disorder. A refined multiexciton model that includes static disorder is applied to fit the experimental power-dependent transient absorption spectra of aqueous protochlorophyllide and the kinetics for delay times up to 20 ps after photoexcitation. We show that population up to the 4-exciton manifold is sufficient to explain the pronounced saturation of the bleaching and the shape changes in the instantaneous, t = 0.2 ps transient spectra when the pulse energy is increased from 10 to 430 nJ per pulse. The decay of the multiexciton manifold is relatively slow and is preceded by a spectroscopically distinct process. We suggest that the exciton states in the Pchlide aggregates are mixed with charge-transfer states (CTS) and that the population and repopulation of the CTS coupled to the exciton states explains the relatively slow decay of the multiexciton manifold. The relevance of our results to the optical properties and dynamics of natural photosynthetic complexes and the possible physical origin of CTS formation are discussed. PMID:21936513

  4. Twin-peaks absorption spectra of excess electron in ionic liquids

    NASA Astrophysics Data System (ADS)

    Musat, Raluca M.; Kondoh, Takafumi; Yoshida, Yoichi; Takahashi, Kenji

    2014-07-01

    The solvated electron in room temperature ionic liquids (RTILs) has been the subject of several investigations and several reports exist on its nature and absorption spectrum. These studies concluded that the solvated electron exhibits an absorption spectrum peaking in the 1000-1400 nm region; a second absorption band peaking in the UV region has been assigned to the hole or dication radicals simultaneously formed in the system. Here we report on the fate of the excess electron in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, P14+/NTf2- using nanosecond pulse radiolysis. Scavenging experiments allowed us to record and disentangle the complex spectrum measured in P14+/NTf2-. We identified a bi-component absorption spectrum, due to the solvated electron, the absorption maxima located at 1080 nm and around 300 nm, as predicted by previous ab-initio molecular dynamics simulations for the dry excess electron. We also measured the spectra using different ionic liquids and confirmed the same feature of two absorption peaks. The present results have important implications for the characterization of solvated electrons in ionic liquids and better understanding of their structure and reactivity.

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

    PubMed Central

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

    2015-01-01

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

  6. Micro-X-ray absorption near edge structure as a suitable probe to monitor live organisms

    NASA Astrophysics Data System (ADS)

    Oger, Phil M.; Daniel, I.; Simionovici, A.; Picard, A.

    2008-04-01

    X-ray spectroscopies are very powerful tools to determine the chemistry of complex dilute solutes in abiotic and biotic systems. We have assayed their suitability to monitor the chemistry of complex solutions in a live biotic system. The impact of the probe on cells was quantified for 4 different cellular organisms differing in their resistance level to environmental stresses. We show that none of the organisms tested can survive the radiation doses needed for the acquisition of meaningful spectroscopic data. Therefore, on one hand, X-ray spectroscopy cannot be applied to the monitoring of single cells, and cellular damages have to be taken into account in the interpretation of the evolution of such systems. On the other hand, due to the limited extension of X-ray induced cellular damages in the culture volume, it is possible to probe a population of live cells provided that the culture to beam probe ratio is large enough to minimize the impact of mortality on the evolution of the biological system. Our results suggest that it could be possible to probe the volume in the close vicinity of a cell without affecting its activity. Using this setup we could monitor the reduction of selenite by the X-ray sensitive bacterium, Agrobacterium tumefaciens strain C58, for 24 h. This method has a great potential to monitor the respiration of various metals, such as iron, manganese and arsenic, in situ under relevant environmental conditions by live microorganisms.

  7. Absorption spectra and photoresponse observation of Cu2O thin film photoanodes

    NASA Astrophysics Data System (ADS)

    Mani, Endri; Garuthara, Rohana

    2014-03-01

    Electrodeposition was used to deposit Cu2O thin films on ITO substrates. The deposited Cu2O films were characterized by photocurrent, absorption and reflectance spectroscopy. Photoresponse of the film clearly indicated n-type behavior of Cu2O in photoelectrochemical cells. The effects of chlorine doped photoanodes deposited in different solution pH on the magnitude of their photocurrent are studied. The low temperature absorption spectra of chlorine doped Cu2O films are found to depend on the solution pH in the range 10.0-7.5. Optical absorption spectra of Cu2O films were measured in the temperature range 79K - 295K. The Urbach's tail was observed for n-type conductive Cu2O films in the temperature range 79K to 295K. The Urbach's energy as a function of temperature for Cu2O films were studied. The results will be discussed with emphasis on the reflectance, absorption and photoresponse observation.

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

    PubMed

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

    2015-06-01

    We use the TDDFT/PBE0/6-31+G* method to determine the electronic absorption and emission energies, in different media, of the four forms of tocopherol, which differ by the number and the position of methyl groups on the chromanol. Geometries of the ground state S0 and the first singlet excited state S1 were optimized in the gas phase, and various solvents. The solvent effect is evaluated using an implicit solvation model (IEF-PCM). Our results are compared to the experimental ones obtained for the vitamin E content in several vegetable oils. For all forms of tocopherols, the HOMO-LUMO first vertical excitation is a π-π* transition. Gas phase and non-polar solvents (benzene and toluene) give higher absorption wavelengths than polar solvents (acetone, ethanol, methanol, DMSO, and water); this can be interpreted by a coplanarity between the O-H group and the chroman, allowing a better electronic resonance of the oxygen lone pairs and the aromatic ring, and therefore giving an important absorption wavelength, whereas the polar solvents give high emission wavelengths comparatively to gas phase and non-polar solvents. Fluorescence spectra permit the determination, the separation, and the identification of the four forms of tocopherols by a large difference in emission wavelength values. Graphical Abstract Scheme from process methodological to obtain the absorption and emission spectra for tocopherols. PMID:26026299

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Kazanas, D.

    1984-01-01

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

  11. NOTE: Absorption spectra variations of EBT radiochromic film from radiation exposure

    NASA Astrophysics Data System (ADS)

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

    2005-07-01

    Gafchromic EBT radiochromic film is one of the newest radiation-induced auto-developing x-ray analysis films available for therapeutic radiation dosimetry in radiotherapy applications. The spectral absorption properties in the visible wavelengths have been investigated and results show two main peaks in absorption located at 636 nm and 585 nm. These absorption peaks are different to many other radiochromic film products such as Gafchromic MD-55 and HS film where two peaks were located at 676 nm and 617 nm respectively. The general shape of the absorption spectra is similar to older designs. A much higher sensitivity is found at high-energy x-rays with an average 0.6 OD per Gy variation in OD seen within the first Gy measured at 636 nm using 6 MV x-rays. This is compared to approximately 0.09 OD units for the first Gy at the 676 nm absorption peak for HS film at 6 MV x-ray energy. The film's blue colour is visually different from older varieties of Gafchromic film with a higher intensity of mid-range blue within the film. The film provides adequate relative absorbed dose measurement for clinical radiotherapy x-ray assessment in the 1 2 Gy dose range which with further investigation may be useful for fractionated radiotherapy dose assessment.

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  13. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

  15. Time variations of narrow absorption lines in high resolution quasar spectra

    NASA Astrophysics Data System (ADS)

    Boissé, P.; Bergeron, J.; Prochaska, J. X.; Péroux, C.; York, D. G.

    2015-09-01

    Aims: We have searched for temporal variations of narrow absorption lines in high resolution quasar spectra. A sample of five distant sources were assembled, for which two spectra are available, either VLT/UVES or Keck/HIRES, which were taken several years apart. Methods: We first investigate under which conditions variations in absorption line profiles can be detected reliably from high resolution spectra and discuss the implications of changes in terms of small-scale structure within the intervening gas or intrinsic origin. The targets selected allow us to investigate the time behaviour of a broad variety of absorption line systems by sampling diverse environments: the vicinity of active nuclei, galaxy halos, molecular-rich galaxy disks associated with damped Lyα systems, as well as neutral gas within our own Galaxy. Results: Intervening absorption lines from Mg ii, Fe ii, or proxy species with lines of lower opacity tracing the same kind of (moderately ionised) gas appear in general to be remarkably stable (1σ upper limits as low as 10% for some components on scales in the range 10-100 au), even for systems at zabs ≈ ze. Marginal variations are observed for Mg ii lines towards PKS 1229-021 at zabs = 0.83032; however, we detect no systems that display any change as large as those reported in low resolution SDSS spectra. The lack of clear variations for low β Mg ii systems does not support the existence of a specific population of absorbers made of swept-up gas towards blazars. In neutral or diffuse molecular media, clear changes are seen for Galactic Na i lines towards PKS 1229-02 (decrease in N by a factor of four for one of the five components over 9.7 yr), corresponding to structure on a scale of about 35 au, in good agreement with known properties of the Galactic interstellar medium. Tentative variations are detected for H2J = 3 lines towards FBQS J2340-0053 at zabs = 2.05454 (≃35% change in column density, N, over 0.7 yr in the rest frame), suggesting

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

    USGS Publications Warehouse

    Kokaly, Raymond F.; Skidmore, Andrew K

    2015-01-01

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

  17. Interplay between structural and electronic properties of various fullerene derivatives, and their absorption spectra

    NASA Astrophysics Data System (ADS)

    Park, Sora; Ahn, Jeung Sun; Kwon, Young-Kyun

    2011-03-01

    Using density functional theory (DFT), we investigate the geometrical structures and electronic properties of various fullerene derivatives formed by attaching several kinds of addends on C60 through [2+2] cycloaddition. Various forms of such derivatives are modeled by considering different kinds, different positions and different numbers of addends to study how structural configurations will affect their electronic structures. Our results reveal that some derivatives with certain symmetries determined by the configuration of addends may have wider energy gap than that of pristine C60 . This suggests that absorption properties could be adjusted by controlling the addends configurations. To describe the excited state properties, such as absorption spectra, of various C60 derivatives more accurately, we performed time-dependent (TD) DFT calculations. We find the position and the intensity of the peak of absorption spectra of derivatives are affected by the specific symmetry of the derivatives defined by the configurations of the addends. To explore such peculiar effects, we analyze the charge distribution and orbital mixing characters.

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

    PubMed

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

    2014-09-01

    Acquiring accurate visible and near-infrared (VisNIR) reflectance values of atmosphereless celestial bodies is very important in inferring the physical and geological properties of their surficial materials. When a calibration target with inherent non-trivial absorption features is used, the calibrated reflectance would essentially always contain spurious spectral features and the spectroscopic data may easily be misinterpreted if the artifact is not properly taken care of. We demonstrate with laboratory reflectance measurements that the VisNIR spectra of three typical planetary surface analog materials, lunar simulant JSC-1A, olivine and pyroxene grains, have an artificial peak at 2.1 µm when Spectralon-type plaque made of polytetrafluoroethylene is used as the calibration target in the NIR region. The degree of severity of this artifact is dependent on the strength of the 2.0 µm absorption feature of the mineral. Empirical methods are proposed to remove this artifact to bring the spectra close to that calibrated by a gold mirror which does not have any conspicuous absorption features in the NIR region. The correction methods may be applied to reflectance data acquired by the VisNIR imaging spectrometer onboard the Yutu Rover of the Chinese Chang'E 3 lunar mission which employed an onboard Spectralon-type calibration target. PMID:25321507

  19. Measurability of Kinetic Temperature from Metal Absorption-Line Spectra Formed in Chaotic Media

    NASA Astrophysics Data System (ADS)

    Levshakov, Sergei A.; Takahara, Fumio; Agafonova, Irina I.

    1999-06-01

    We present a new method for recovering the kinetic temperature of the intervening diffuse gas to an accuracy of 10%. The method is based on the comparison of unsaturated absorption-line profiles of two species with different atomic weights. The species are assumed to have the same temperature and bulk motion within the absorbing region. The computational technique involves the Fourier transform of the absorption profiles and the consequent entropy-regularized χ2-minimization (ERM) to estimate the model parameters. The procedure is tested using synthetic spectra of C+, Si+, and Fe+ ions. The comparison with the standard Voigt fitting analysis is performed, and it is shown that the Voigt deconvolution of the complex absorption-line profiles may result in estimated temperatures that are not physical. We also successfully analyze Keck telescope spectra of C II λ1334 and Si II λ1260 lines observed at the redshift z=3.572 toward the quasar Q1937-1009 by Tytler et al. Based in part on data obtained at the W. M. Keck Observatory, which is jointly operated by the University of California and the California Institute of Technology.

  20. Spectra extraction for wavelength-modulation spectroscopy of intra-cavity absorption gas sensor

    NASA Astrophysics Data System (ADS)

    Han, Wennian; Wang, Yan; Liu, Kun; Jia, Dagong; Liu, Tiegen

    2010-11-01

    Low-frequency wavelength modulation is introduced to increase sensitivity of intra-cavity absorption gas sensor (ICAGS) system. ICAGS system including erbium-doped fiber amplifier (EDFA), pump laser, tunable fiber Fabry-Perot (F-P) optical filter and gas cell is set up. Using virtual instrument technique, modulation function is generated by LabVIEW software and outputted through the AO ports of data acquisition card to tune the driving voltage of optical filter. The AI ports collect the laser power signals in a synchronous mode. Harmonic spectra can be computed by adopting the method of the Discrete Fourier Transform (DFT). According to the characteristics of different order harmonic, even harmonics and odd harmonics are analyzed respectively. Here, second harmonic is used to determine the spectral intensity, and third harmonic is mainly used to locate the position of spectral lines. With optimum 10 Hz frequency modulation, acetylene absorption experiments were carried out. The pump current of EDFA is 60 mA and the acetylene concentration in the gas cell is 1%. After spectra extraction, in the 1526 nm to 1537 nm wavelength range, 17 absorption lines of acetylene were achieved. The results indicated that the error of wavelength position is less than 0.1 nm and the minimum detection limit of acetylene is about 120x10-6. It is possible to realize the recognition of measured gas type and multi-component gas detection for ICAGS system.

  1. Vibronic bandshape of the absorption spectra of dibenzoylmethanatoboron difluoride derivatives: analysis based on ab initio calculations.

    PubMed

    Rukin, Pavel S; Freidzon, Alexandra Ya; Scherbinin, Andrei V; Sazhnikov, Vyacheslav A; Bagaturyants, Alexander A; Alfimov, Michael V

    2015-07-14

    The nature of absorption bandshapes of dibenzoylmethanatoboron difluoride (DBMBF2) dye substituted in ortho-, meta-, and para-positions of the phenyl ring is investigated using DFT and TDDFT with the range-separated hybrid CAM-B3LYP functional and the 6-311G(d,p) basis set. The solvent effects are taken into account within the polarized continuum model. The vibronic bandshape is simulated using a time-dependent linear coupling model with a vertical gradient approach through an original code. For flexible chromophores, the spectra of individual conformers are summed up with Boltzmann factors. It is shown that the long-wavelength absorption bandshape of DBMBF2 derivatives is determined by three factors: the relative statistical weights of conformers with different electronic absorption patterns, the relative position and intensity of the second low-energy electronic transition, and the vibronic structure of individual electronic peaks. The latter is governed by the relationship between the hard vibrational modes, which contribute to vibronic progression, and soft modes, which provide broadening of the peaks. The simulated spectra of the dyes in the study are generally consistent with the available experimental data and explain the observed spectral features. PMID:26062782

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

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

    SciTech Connect

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

    2008-03-28

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

  4. Measurement of Gas and Aerosol Phase Absorption Spectra across the Visible and Near-IR Using Supercontinuum Photoacoustic Spectroscopy.

    PubMed

    Radney, James G; Zangmeister, Christopher D

    2015-07-21

    We demonstrate a method to measure the absorption spectra of gas and aerosol species across the visible and near-IR (500 to 840 nm) using a photoacoustic (PA) spectrometer and a pulsed supercontinuum laser source. Measurements of gas phase absorption spectra were demonstrated using H2O(g) as a function of relative humidity (RH). The measured absorption intensities and peak shapes were able to be quantified and compared to spectra calculated using the 2012 High Resolution Transmission (HITRAN2012) database. Size and mass selected nigrosin aerosol was used to measure absorption spectra across the visible and near-IR. Spectra were measured as a function of aerosol size/mass and show good agreement to Mie theory calculations. Lastly, we measured the broadband absorption spectrum of flame generated soot aerosol at 5% and 70% RH. For the high RH case, we are able to quantifiably separate the soot and water absorption contributions. For soot, we observe an enhancement in the mass specific absorption cross section ranging from 1.5 at 500 nm (p < 0.01) to 1.2 at 840 nm (p < 0.2) and a concomitant increase in the absorption Ångström exponent from 1.2 ± 0.4 (5% RH) to 1.6 ± 0.3 (70% RH). PMID:26098142

  5. Infrared absorption and vibrational circular dichroism spectra of poly(vinyl ether) containing diastereomeric menthols as pendants

    NASA Astrophysics Data System (ADS)

    McCann, Jennifer L.; Rauk, Arvi; Wieser, Hal

    1997-06-01

    The absorption and vibrational circular dichroism (VCD) spectra in the 1700 to 830 cm -1 region are reported and qualitatively interpreted for poly(vinyl ether) with (+)-menthol (I), (+)-isomenthol (II) and (+)-neomenthol (III) as pendants.

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

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

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

  7. Dielectric tensor of tetracene single crystals: the effect of anisotropy on polarized absorption and emission spectra.

    PubMed

    Tavazzi, S; Raimondo, L; Silvestri, L; Spearman, P; Camposeo, A; Polo, M; Pisignano, D

    2008-04-21

    The full UV-visible dielectric tensor and the corresponding directions of the principal axes of triclinic tetracene crystals are reported as deduced either by polarized absorption and ellipsometry measurements or by calculations based on the molecular and crystallographic data. The results allow the attribution of the polarized bands observed in both absorption and photoluminescence emission spectra. In particular, the spectral line shape and polarization of the emission are found to depend on the sample thickness, and the effect is attributed to the modification of the state of polarization of the emitted light during its propagation inside the crystal. Indeed, the directions of polarization of the lowest optical transitions and the directions of the principal axes of the dielectric tensor are demonstrated not to coincide, in contrast to the assumptions typically made in the literature, thus causing the mixed transverse/longitudinal character of light propagation. PMID:18433260

  8. Index of Refraction and Absorption Coefficient Spectra of Paratellurite in the Terahertz Region

    NASA Astrophysics Data System (ADS)

    Unferdorben, Márta; Buzády, Andrea; Hebling, János; Kiss, Krisztián; Hajdara, Ivett; Kovács, László; Péter, Ágnes; Pálfalvi, László

    2016-07-01

    Index of refraction and absorption coefficient spectra of pure paratellurite (α-TeO2) crystal as a potential material for terahertz (THz) applications were determined in the 0.25-2 THz frequency range at room temperature by THz time domain spectroscopy (THz-TDS). The investigation was performed with beam polarization both parallel (extraordinary polarization) and perpendicular (ordinary polarization) to the optical axis [001] of the crystal. Similarly to the visible spectral range, positive birefringence was observed in the THz range as well. It was shown that the values of the refractive index for extraordinary polarization are higher and show significantly larger dispersion than for the ordinary one. The absorption coefficient values are also larger for extraordinary polarization. The measured values were fitted by theoretical curves derived from the complex dielectric function containing independent terms of Lorentz oscillators due to phonon-polariton resonances. The results are compared with earlier publications, and the observed significant discrepancies are discussed.

  9. Radiolytically induced formation and optical absorption spectra of colloidal silver nanoparticles in supercritical ethane.

    SciTech Connect

    Dimitrijevic, N. M.; Bartels, D. M.; Jonah, C. D.; Takahashi, K.; Rajh, T.; Chemistry

    2001-02-08

    Colloidal silver nanoparticles were synthesized in supercritical ethane at 80 {sup o}C and 80-120 bar, with methanol as cosolvent. Solvated electrons, produced by a pulse of 20 MeV electrons, reduced the silver ions. The time-resolved technique of pulse radiolysis was employed to characterize the reduction products and colloidal metallic particles. The absorption spectra of small silver clusters (Ag{sub 2}{sup +}, Ag{sub 3}{sup +}, Ag{sub 4}{sup 2+}, etc.) were detected at short times after the pulse. Colloidal metallic silver particles were identified by their characteristic plasmon absorption at 1-10 s after the pulse. Colloidal particles are stable for hours in supercritical ethane. The particles are less than 10 nm in diameter. Their size was determined using transmission electron microscope after precipitation from the solution.

  10. Pressure dependence of Hexanitrostilbene Raman/ electronic absorption spectra to validate DFT EOS

    NASA Astrophysics Data System (ADS)

    Farrow, Darcie; Alam, Kathleen; Martin, Laura; Fan, Hongyou; Kay, Jeffrey; Wixom, Ryan

    2015-06-01

    Due to its thermal stability and low vapor pressure, Hexanitrostilbene (HNS) is often used in high-temperature or vacuum applications as a detonator explosive or in mild detonating fuse. Toward improving the accuracy of the equation of state used in hydrodynamic simulations of the performance of HNS, we have measured the Raman and electronic absorption spectra of this material under static pressure in a diamond anvil cell. Density functional theory calculations were used to simulate the pressure dependence of the Raman/Electronic spectra along the Hugoniot and 300K isotherm for comparison and to aid in interpreting the data. We will discuss changes in the electronic structure of HNS under pressure, validation of a DFT predicted equation of state (EOS), and using this data as a basis for understanding future pulsed Raman measurements on dynamically compressed HNS samples.

  11. The Intervening Galaxies Hypothesis of the Absorption Spectra of Quasi-Stellar Objects: Some Statistical Studies

    NASA Astrophysics Data System (ADS)

    Duari, Debiprosad; Narlikar, Jayant V.

    This paper examines, in the light of the available data, the hypothesis that the heavy element absorption line systems in the spectra of QSOs originate through en-route absorption by intervening galaxies, halos etc. Several statistical tests are applied in two different ways to compare the predictions of the intervening galaxies hypothesis (IGH) with actual observations. The database is taken from a recent 1991 compilation of absorption line systems by Junkkarinen, Hewitt and Burbidge. Although, prima facie, a considerable gap is found between the predictions of the intervening galaxies hypothesis and the actual observations despite inclusion of any effects of clustering and some likely selection effects, the gap narrows after invoking evolution in the number density of absorbers and allowing for the incompleteness and inhomogeneity of samples examined. On the latter count the gap might be bridgeable by stretching the parameters of the theory. It is concluded that although the intervening galaxies hypothesis is a possible natural explanation to account for the absorption line systems and may in fact do so in several cases, it seems too simplistic to be able to account for all the available data. It is further stressed that the statistical techniques described here will be useful for future studies of complete and homogenous samples with a view to deciding the extent of applicability of the IGH.

  12. IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

    NASA Astrophysics Data System (ADS)

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

    2007-01-01

    We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering.

  13. Atomic calculations and search for variation of the fine-structure constant in quasar absorption spectra

    NASA Astrophysics Data System (ADS)

    Dzuba, V. A.; Flambaum, V. V.

    A brief review of the search for variation of the fine structure constant in quasar absorption spectra is presented. Special consideration is given to the role of atomic calculations in the analysis of the observed data. A range of methods which allow to perform calculations for atoms or ions with different electron structure and which cover practically all periodic table of elements is discussed. Critical compilation of the results of the calculations as well as a review of the most recent results of the analysis are presented.

  14. Decay heat and anti-neutrino energy spectra in fission fragments from total absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Rykaczewski, Krzysztof

    2015-10-01

    Decay studies of over forty 238U fission products have been studied using ORNL's Modular Total Absorption Spectrometer. The results are showing increased decay heat values, by 10% to 50%, and the energy spectra of anti-neutrinos shifted towards lower energies. The latter effect is resulting in a reduced number of anti-neutrinos interacting with matter, often by tens of percent per fission product. The results for several studied nuclei will be presented and their impact on decay heat pattern in power reactors and reactor anti-neutrino physics will be discussed.

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

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

  16. Water vapor absorption spectra of the upper atmosphere (45-185 cm(-1)).

    PubMed

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

    1975-09-01

    The far ir nighttime absorption spectrum of the earth's atmosphere above 14 km is determined from observations of the bright moon. The spectra were obtained using a Michelson interferometer attached to a 30-cm telescope aboard a high-altitude jet aircraft. Comparison with a single-layer model atmosphere implies a vertical column of 3.4 +/- 0.4 mum of percipitable water on 30 August 1971 and 2.4 +/- 0.3 mum of precipitable water on 6 January 1972. PMID:20154976

  17. Absorption spectra of riboflavin--a difficult case for computational chemistry.

    PubMed

    Wu, Min; Eriksson, Leif A

    2010-09-23

    Computing accurate absorption spectra of riboflavin (RBF) has proven a difficult task for computational chemistry. Time-dependent density functional theory have herein been employed using a wide range of recent range-separated and hybrid meta functionals to investigate ultraviolet and visible spectra of RBF to determine if any progress has been made through recent developments. It is concluded that B3LYP and PBE0 perform the best throughout the entire test set. However, since all methods deviate from experimental results by at least 40 nm when computing the spectra in vacuum, two approaches to describe aqueous solution are implemented together with the MPWB1K, B3LYP, and PBE0 functionals: implicitly using integral equation formulation of the polarized continuum model (minor improvement) and explicitly through molecular dynamics (MD) simulations of the molecule embedded in a water cluster whereafter snapshots of RBF-water clusters are extracted and time-dependent density functional theory calculations performed. The resulting averaged spectra from the MD-simulated clusters show a constant blue-shift for all peaks by ∼20 nm compared to experimental data at the TD-B3LYP/6-31+G(d,p) level. PMID:20718485

  18. The X-shooter sample of GRB afterglow spectra: Properties of the absorption features

    NASA Astrophysics Data System (ADS)

    de Ugarte Postigo, Antonio

    2015-08-01

    Since its commissioning at ESO's Very Large Telescope in 2009, the X-shooter spectrograph has become the reference instrument in gamma-ray burst (GRB) afterglow spectroscopy. During this time our collaboration has collected more than 70 spectra of GRB afterglows, with redshifts ranging from 0.06 to 6.3. Thanks to their extreme luminosity and simple intrinsic shape, GRB spectra are optimal tools for the study of galactic environments at basically any redshift. Being produced by the death of short-lived massive stars, they are also tracers of star formation.I will present the sample of absorption spectral features identified in X-shooter's GRB spectra describing observation and analysis techniques. The different features are compared with the characteristics of the explosion (duration, spectral shape, energetics, etc.) and with the properties of the host galaxy (mass, age, etc.) to improve our understanding of the nature of the explosions and how they interact with their environments. Using the large redshift range of the spectra collection we perform studies of the evolution of GRB environments across the history of the Universe and their relation with the evolution of star formation.

  19. Appraisal of Surface Hopping as a Tool for Modeling Condensed Phase Linear Absorption Spectra.

    PubMed

    Petit, Andrew S; Subotnik, Joseph E

    2015-09-01

    Whereas surface hopping is usually used to study populations and mean-field dynamics to study coherences, in two recent papers, we described a procedure for calculating dipole-dipole correlation functions (and therefore absorption spectra) directly from ensembles of surface hopping trajectories. We previously applied this method to a handful of one-dimensional model problems intended to mimic the gas phase. In this article, we now benchmark this new procedure on a set of multidimensional model problems intended to mimic the condensed phase and compare our results against other standard semiclassical methods. By comparison, we demonstrate that methods that include only dynamical information from one PES (the standard Kubo approaches) exhibit large discrepancies with the results of exact quantum dynamics. Furthermore, for model problems with nonadiabatic excited state dynamics but no quantized vibrational structure in the spectra, our surface hopping approach performs comparably to using Ehrenfest dynamics to calculate the electronic coherences. That being said, however, when quantized vibrational structures are present in the spectra but the electronic states are uncoupled, performing the dynamics on the mean PES still outperforms our present method. These benchmark results should influence future studies that use ensembles of independent semiclassical trajectories to model linear as well as multidimensional spectra in the condensed phase. PMID:26575927

  20. Determination of phosphorus using high-resolution diphosphorus molecular absorption spectra produced in the graphite furnace

    NASA Astrophysics Data System (ADS)

    Huang, Mao Dong; Becker-Ross, Helmut; Okruss, Michael; Geisler, Sebastian; Florek, Stefan

    2016-01-01

    Molecular absorption of diphosphorus was produced in a graphite furnace and evaluated in view of its suitability for phosphorus determination. Measurements were performed with two different high-resolution continuum source absorption spectrometers. The first system is a newly in-house developed simultaneous broad-range spectrograph, which was mainly used for recording overview absorption spectra of P2 between 193 nm and 245 nm. The region covers the main part of the C 1Σu+ ← X 1Σg+ electronic transition and shows a complex structure with many vibrational bands, each consisting of a multitude of sharp rotational lines. With the help of molecular data available for P2, an assignment of the vibrational bands was possible and the rotational structure could be compared with simulated spectra. The second system is a commercial sequential continuum source spectrometer, which was used for the basic analytical measurements. The P2 rotational line at 204.205 nm was selected and systematically evaluated with regard to phosphorus determination. The conditions for P2 generation were optimized and it was found that the combination of a ZrC modified graphite tube and borate as a chemical modifier were essential for a good production of P2. Serious interferences were found in the case of nitrate and sulfuric acid, although the nitrate interference can be eliminated by a higher pyrolysis temperature. The reliability of the method was proved by analysis of certified samples. Using standard tubes, a characteristic mass of 10 ng and a limit of detection of 7 ng were found. The values could further be improved by a factor of ten using a miniaturized tube with an internal diameter of 2 mm. Compared to the conventional method based on the phosphorus absorption line at 213.618 nm, the advantages of using P2 are the gentle temperature conditions and the potential of performing a simultaneous multi-line evaluation to further improve the limit of detection.

  1. Picosecond kinetics and Sn <-- S1 absorption spectra of retinoids and carotenoids

    NASA Astrophysics Data System (ADS)

    Bondarev, Stanislav L.; Tikhomirov, S. A.; Bachilo, Sergei M.

    1991-05-01

    Light energy absorption, as well as the subsequent photochemical and photophysical processes of cis -+trans isomerisation (vision and bacteriorhodopsin photosynthesis) and energy transfer (photosynthesis in green plants and micro organisms) take place in a pigment-protein complex including polyene chromophors, retinoids and carotenoids. Picosecond and subpicosecond studies of the spectral and kinetic characteristics of these processes are carried out in both complex photoreceptor and photosynthetic ms'2 and model systems with the use of solutions of retinoids and carotenoids.36 The lifetimes of the lower singlet-exited states S (21A; ) ofsome carotenoids in toluene at room temperature have been measured by the method of picosecond photolysis and amount to 8.6+/- 0.5 for all-trans-fl -carotene1 and 5.2 0.6 PS for canthaxanthin.5 /3 -carotene fluorescence at room temperature is practically absent, its yield being less than iO (Ref. 7). /1 -carotene fluorescence at 77 and 4.2 K in isopentane discovered by us8 is characterized by yields of (4+/-2) .iO and (8+/-3) . i0- and lifetimes of(4+/-2) .iO' and (8+/-3) .iO' and is due to the transitions from the higher S(1' B) state. The picosecond transient S -S absorption of/I - carotene in different solvents at 293 K is characterized by spectra in the 550-600 nm range.8 For retinoids, there is one work (Ref. 4) which gives the S, +-Si absorption spectrum of the Schiff base (aldimine) of retinal with amaz 465 mn in n-hexane at 290 K. The duration of transient absorption was 21 5 ps, although the fluorescence kinetics measured in this work (Ref. 4) at 298 K were characterized by two-component decay with r1 = 22 and r2 = 265 ps. The transient picosecond absorption spectra for retinal are absent in the literature and the lifetimes of its singlet-excited state at room temperature, measured by absorption and fluorescence, amount to 20+/-10 Ps in n-hexane3 and 17 Ps in ethanol,'9 respectively.

  2. Absorption in X-ray spectra of high-redshift quasars

    NASA Technical Reports Server (NTRS)

    Elvis, Martin; Fiore, Fabrizio; Wilkes, Belinda; Mcdowell, Jonathan; Bechtold, Jill

    1994-01-01

    We present evidence that X-ray absorption is common in high-redshift quasars. We have studied six high-redshift (z approximately 3) quasars with the ROSAT Position Sensitive Proportional Counter (PSPC) of which four are in directions of low Galactic N(sub H). Three out of these four show excess absorption, while only three in approximately 50 z approximately less than 0.4 quasars do, indicating that such absorption must be common, but not ubiquitous, at high redshifts, and that the absorbers must lie at z greater than 0.4. The six quasars were: S5 0014+81, Q0420-388, PKS 0438-436, S4 0636+680. PKS 2000-330, PKS 2126-158, which have redshifts between 2.85 and 3.78. PKS 0438-436 and PKS 2126-158 show evidence for absorption above the local Galactic value at better than 99.999% confidence level. If the absorber is at the redshift of the quasar, then values of N(sub H) = (0.86(+0.49, -0.28)) x 10(exp 22) atoms/sq cm for PKS 0438-436, and N(sub H) = (1.45(+1.20, -0.64)) x 10(exp 22) atoms/ sq cm for PKS 2126-158, are implied, assuming solar abundances. The spectrum of S4 0636+680 also suggests the presence of a similarly large absorption column density at the 98% confidence level. This absorption reverses the trend for the most luminous active galactic nuclei (AGN) to have the least X-ray absorption, so a new mechanism is likely to be responsible. Intervening absorption due to damped Lyman(alpha) systems is a plausible cause. We also suggest, as an intrinsic model, that intracluster material, e.g., a cooling flow, around the quasar could account for both the X-ray spectrum and other properties of these quasars. All the quasars are radio-loud and three are gigahertz peaked (two of the three showing absorption). No excess absorption above the Galactic value is seen toward Q0420-388. This quasar has two damped Lyman(alpha) systems at z = 3.08. The limit on the X-ray column density implies a low ionization fraction, N(H I)/N(H) approximately greater than 4 x 10(exp -3) (3

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

  4. Aprotic solvents effect on the UV-visible absorption spectra of bixin.

    PubMed

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-15

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0→S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration. PMID:24840486

  5. A wavelet analysis for the X-ray absorption spectra of molecules

    SciTech Connect

    Penfold, T. J.; Tavernelli, I.; Rothlisberger, U.; Milne, C. J.; Abela, R.; Reinhard, M.; Nahhas, A. El; Chergui, M.

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  6. Understanding the absorption and emission spectra of borondipyrromethene dye and its substituted analogues

    NASA Astrophysics Data System (ADS)

    Nithya, R.; Kolandaivel, P.; Senthilkumar, K.

    2012-04-01

    Borondipyrromethene (BODIPY) dye possesses a bright and long wavelength emitting fluorescent character with a wide spectral range from visible to near infrared region. In the present work, the spectral properties of BODIPY dyes were analyzed using ab intio and density functional theory methods. The ground and excited state geometries of BODIPY and its substituted analogues in chloroform medium, were optimized using the density functional theory (DFT) and singly excited configuration interaction (CIS) methods. Based on the ground and excited state geometries, the absorption and emission spectra have been calculated using time-dependent density functional theory (TDDFT) method. The TDDFT calculations have been performed using hybrid exchange correlation functionals B3LYP and M06-HF and long-range separated functionals LC-BLYP, LC-BOP, LC-PBE, LC-PBE0 and CAM-B3LYP. The solvent phase calculations were carried out using polarizable continuum model (PCM). The TDDFT investigation reveals that the substitution of acceptor, donor-donor, donor-acceptor-donor and phenyl group in BODIPY dye influence the absorption and emission spectra significantly.

  7. Aprotic solvents effect on the UV-visible absorption spectra of bixin

    NASA Astrophysics Data System (ADS)

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-01

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0 → S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration.

  8. Multi-state extrapolation of UV/Vis absorption spectra with QM/QM hybrid methods

    NASA Astrophysics Data System (ADS)

    Ren, Sijin; Caricato, Marco

    2016-05-01

    In this work, we present a simple approach to simulate absorption spectra from hybrid QM/QM calculations. The goal is to obtain reliable spectra for compounds that are too large to be treated efficiently at a high level of theory. The present approach is based on the extrapolation of the entire absorption spectrum obtained by individual subcalculations. Our program locates the main spectral features in each subcalculation, e.g., band peaks and shoulders, and fits them to Gaussian functions. Each Gaussian is then extrapolated with a formula similar to that of ONIOM (Our own N-layered Integrated molecular Orbital molecular Mechanics). However, information about individual excitations is not necessary so that difficult state-matching across subcalculations is avoided. This multi-state extrapolation thus requires relatively low implementation effort while affording maximum flexibility in the choice of methods to be combined in the hybrid approach. The test calculations show the efficacy and robustness of this methodology in reproducing the spectrum computed for the entire molecule at a high level of theory.

  9. Multi-state extrapolation of UV/Vis absorption spectra with QM/QM hybrid methods.

    PubMed

    Ren, Sijin; Caricato, Marco

    2016-05-14

    In this work, we present a simple approach to simulate absorption spectra from hybrid QM/QM calculations. The goal is to obtain reliable spectra for compounds that are too large to be treated efficiently at a high level of theory. The present approach is based on the extrapolation of the entire absorption spectrum obtained by individual subcalculations. Our program locates the main spectral features in each subcalculation, e.g., band peaks and shoulders, and fits them to Gaussian functions. Each Gaussian is then extrapolated with a formula similar to that of ONIOM (Our own N-layered Integrated molecular Orbital molecular Mechanics). However, information about individual excitations is not necessary so that difficult state-matching across subcalculations is avoided. This multi-state extrapolation thus requires relatively low implementation effort while affording maximum flexibility in the choice of methods to be combined in the hybrid approach. The test calculations show the efficacy and robustness of this methodology in reproducing the spectrum computed for the entire molecule at a high level of theory. PMID:27179466

  10. Absorption and spectra of optical parameters in amorphous solid solutions of the Se-S system

    SciTech Connect

    Djalilov, N. Z.; Damirov, G. M.

    2011-04-15

    A study of the optical properties of the Se-S system has revealed a correlation between the dependences of optical absorption coefficient {alpha}, effective concentration of charged defects N{sub t}, and characteristic energy E{sub 0} corresponding to the Urbach optical absorption in the spectral region where the Urbach rule works for the Se-S system on the S concentration. These optical properties are controlled by charged defects. It is shown that concentrations of intrinsic charged defects can be changed by variation in composition of the Se-S system. Reflectance spectra of amorphous solid solutions of the Se-S system are studied within the energy range 1-6 eV. Using the Kramers-Kronig method, spectral dependences of optical constants and derivative optical and dielectric functions are calculated. Variation in the spectra of optical parameters with composition of the Se-S system are explained within a cluster model in which the density of electron states is a function of atomic configurations in clusters, i.e., of the character of a short-range order.

  11. Plasmonic resonance absorption spectra in mid-infrared in an array of graphene nanoresonators

    NASA Astrophysics Data System (ADS)

    Abeysinghe, Don C.; Myers, Joshua; Nader Esfahani, Nima; Hendrickson, Joshua R.; Cleary, Justin W.; Walker, Dennis E.; Chen, Kuei-Hsien; Chen, Li-Chyong; Mou, Shin

    2013-12-01

    We experimentally demonstrated graphene plasmon resonant absorption in mid-IR by utilizing an array of graphene nanoribbon resonators on SiO2 substrate. By tuning resonator width we probed the graphene plasmons with λp <= λ0/100 and plasmon resonances as high as 0.240 eV (2100 cm-1) for 40 nm wide nanoresonators. Resonant absorption spectra revealed plasmon dispersion as well as plasmon damping due to the interaction of graphene plasmons with the surface polar phonons in SiO2 substrate and intrinsic graphene optical phonons. Graphene nanoribbons with varying widths enabled us to identify the damping mechanisms of graphene plasmons and much reduced damping was observed when the plasmon resonance frequencies were close to the substrate polar phonon frequencies. Then, by direct ebeam exposure of graphene nanoresonators, we effectively changed the carrier density and caused red-shift of the plasmon spectra. This work will provide insight into light-sensitive, frequency-tunable photodetectors based on graphene's plasmonic excitations.

  12. Exciton-Like Behavior in Low-Energy Absorption Spectra of Simple Alloys

    NASA Astrophysics Data System (ADS)

    Bakshi, Mira Hemendraray

    The valence excitation (ns('2) (--->) nsnp) spectra of Mg, Zn, and Ca impurities at various concentrations in Li have been measured. Polarization modulation ellipsometry was used to determine the impurity-induced changes in real and imaginary parts of the dielectric function simultaneously, together with the differential reflectivity, in the energy range 1.5 - 4.5 eV. The most important result at sufficiently dilute alloy compositions, is that the system investigated display a distinct absorption peak above the Drude background. The height of this peak varies linearly with impurity content. The impurity-specific character of these spectral features points to exciton-like behavior at low-energy, arising from atomic-like excitations in which the electron and the hole linger together at the impurity site. Existing theories of alloy spectra do not explain these effects, because they do not include the Coulomb correlations between the interacting quasiparticles created in the optical event, or the way in which the interacting pair is confined to the impurity site by the mutual field. A remarkable added result of this research is that the exciton-like behavior can be followed with increasing impurity content, all the way to the pure Mg response, when it becomes the interband transition. This has led Kunz and Flynn to reformulate the theory of optical absorption including excited state interactions; and to apply the theory to the spectrum of pure Mg. The Coulomb interaction causes striking effects which are in generally good agreement with experiment. Zn-Li alloys behave differently. At an alloy composition for which Zn-Zn interactions become prevalent, the local, impurity-specific character of the spectrum disappears, leaving only a featureless Drude-like absorption. These results have provoked cluster calculations by Boisvert and Kunz, which predict the spectral shifts, and exhibit qualitatively similar persistence for Mg-Li, and broadening for Zn-Li.

  13. Excitation dynamics in Phycoerythrin 545: modeling of steady-state spectra and transient absorption with modified Redfield theory.

    PubMed

    Novoderezhkin, Vladimir I; Doust, Alexander B; Curutchet, Carles; Scholes, Gregory D; van Grondelle, Rienk

    2010-07-21

    We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex. PMID:20643051

  14. Infrared absorption spectra of a Nd0.5Ho0.5Fe3(BO3)4 crystal

    NASA Astrophysics Data System (ADS)

    Gerasimova, Yu. V.; Sofronova, S. N.; Gudim, I. A.; Oreshonkov, A. S.; Vtyurin, A. N.; Ivanenko, A. A.

    2016-01-01

    Infrared absorption spectra of a Nd0.5Ho0.5Fe3(BO3)4 crystal in the spectral range of 30-1700 cm-1 have been measured at temperatures from 6 to 300 K. The experimental spectra have been analyzed based on the semiempirical calculation of the lattice dynamics and the analysis of correlation diagrams of borate complexes. No changes associated with structural phase transitions have been detected in the temperature range of measurements; the effect of magnetic ordering on the infrared absorption spectra has not been observed.

  15. Orthogonal spectra and cross sections: Application to optimization of multi-spectral absorption and fluorescence lidar

    SciTech Connect

    Shokair, I.R.

    1997-09-01

    This report addresses the problem of selection of lidar parameters, namely wavelengths for absorption lidar and excitation fluorescence pairs for fluorescence lidar, for optimal detection of species. Orthogonal spectra and cross sections are used as mathematical representations which provide a quantitative measure of species distinguishability in mixtures. Using these quantities, a simple expression for the absolute error in calculated species concentration is derived and optimization is accomplished by variation of lidar parameters to minimize this error. It is shown that the optimum number of wavelengths for detection of a species using absorption lidar (excitation fluorescence pairs for fluorescence lidar) is the same as the number of species in the mixture. Each species present in the mixture has its own set of optimum wavelengths. There is usually some overlap in these sets. The optimization method is applied to two examples, one using absorption and the other using fluorescence lidar, for analyzing mixtures of four organic compounds. The effect of atmospheric attenuation is included in the optimization process. Although the number of optimum wavelengths might be small, it is essential to do large numbers of measurements at these wavelengths in order to maximize canceling of statistical errors.

  16. [Laser induced breakdown spectra of coal sample and self-absorption of the spectral line].

    PubMed

    Zhang, Gui-yin; Ji, Hui; Jin, Yi-dong

    2014-12-01

    The LIBS of one kind of household fuel coal was obtained with the first harmonic output 532 nm of an Nd·YAG laser as radiation source. With the assignment of the spectral lines, it was found that besides the elements C, Si, Mg, Fe, Al, Ca, Ti, Na and K, which are reported to be contained in coal, the presented sample also contains trace elements, such as Cd, Co, Hf, Ir, Li, Mn, Ni, Rb, Sr, V, W, Zn, Zr etc, but the spectral lines corresponding to O and H elements did not appear in the spectra. This is owing to the facts that the transition probability of H and O atoms is small and the energy of the upper level for transition is higher. The results of measurement also show that the intensity of spectral line increases with the laser pulse energy and self-absorption of the spectral lines K766.493 nm and K769.921 nm will appear to some extent. Increasing laser energy further will make self-absorption more obvious. The presence of self-absorption can be attributed to two factors. One is the higher transition rate of K atoms, and the other is that the increase in laser intensity induces the enhancement of the particle number density in the plasma. PMID:25881446

  17. Phase speed spectra of transient eddy fluxes and critical layer absorption

    NASA Technical Reports Server (NTRS)

    Randel, William J.; Held, Isaac M.

    1991-01-01

    Tropospheric zonal mean eddy fluxes of heat and momentum, and the divergence of the Eliassen-Palm flux, are decomposed into contributions from different zonal phase speeds. Data analyzed are the European Center for Medium Range Weather Forecasts operational global analyses covering 1980-1987. Eastward moving medium-scale waves (zonal waves 4-7) dominate the spectra of lower tropospheric heat fluxes in both hemispheres and all seasons. Upper tropospheric wave flux spectra are similar to the low level spectra in midlatitudes, but shift to slower zonal phase speeds as low latitudes are approached. The cause of this shift is the selective absorption of faster moving components in midlatitudes as the waves propagate meridionally. Latitude-phase speed distributions of eddy fluxes are constructed and compared to the zonal mean wind structure. These results demonstrate that upper tropospheric eddies break and decelerate the zonal mean flow approximately 10-20 deg in latitude away from their critical line (where phase speed equals zonal wind speed). Comparisons are also made with results from the middle stratosphere.

  18. Shape of the absorption and fluorescence spectra of condensed phases and transition energies.

    PubMed

    Lagos, Miguel; Paredes, Rodrigo

    2014-11-13

    General integral expressions for the temperature-dependent profile of the spectral lines of photon absorption and emission by atomic or molecular species in a condensed environment are derived with no other hypothesis than: (a) The acoustic vibrational modes of the condensed host medium constitute the thermodynamic energy reservoir at a given constant temperature, and local electronic transitions modifying the equilibrium configuration of the surroundings are multiphonon events, regardless of the magnitude of the transition energy. (b) Electron-phonon coupling is linear in the variations of the bond length. The purpose is to develop a theoretical tool for the analysis of the spectra, allowing us to grasp highly accurate information from fitting the theoretical line shape function to experiment, including those spectra displaying wide features. The method is illustrated by applying it to two dyes, Lucifer Yellow CH and Coumarin 1, which display fluorescence maxima of 0.41 and 0.51 eV fwhm. Fitting the theoretical curves to the spectra indicates that the neat excitation energies are 2.58 eV ± 2.5% and 3.00 eV ± 2.0%, respectively. PMID:25321927

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

    SciTech Connect

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

    1986-04-01

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

  20. Stratospheric N2O mixing ratio profile from high-resolution balloon-borne solar absorption spectra and laboratory spectra near 1880/cm

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Smith, M. A. H.; Seals, R. K., Jr.; Larsen, J. C.; Rinsland, P. L.

    1982-01-01

    A nonlinear least-squares fitting procedure is used to derive the stratospheric N2O mixing ratio profile from balloon-borne solar absorption spectra and laboratory spectra near 1880/cm. The atmospheric spectra analyzed here were recorded during sunset from a float altitude of 33 km with the University of Denver's 0.02/cm resolution interferometer near Alamogordo, N.M. (33 deg N) on Oct. 10, 1979. The laboratory data are used to determine the N2O line intensities. The measurements suggest an N2O mixing ratio of 264 ppbv near 15 km, decreasing to 155 ppbv near 28 km.

  1. Absorption-Mode Fourier Transform Mass Spectrometry: The Effects of Apodization and Phasing on Modified Protein Spectra

    NASA Astrophysics Data System (ADS)

    Qi, Yulin; Li, Huilin; Wills, Rebecca H.; Perez-Hurtado, Pilar; Yu, Xiang; Kilgour, David P. A.; Barrow, Mark P.; Lin, Cheng; O'Connor, Peter B.

    2013-06-01

    The method of phasing broadband Fourier transform ion cyclotron resonance (FT-ICR) spectra allows plotting the spectra in the absorption-mode; this new approach significantly improves the quality of the data at no extra cost. Herein, an internal calibration method for calculating the phase function has been developed and successfully applied to the top-down spectra of modified proteins, where the peak intensities vary by 100×. The result shows that the use of absorption-mode spectra allows more peaks to be discerned within the recorded data, and this can reveal much greater information about the protein and modifications under investigation. In addition, noise and harmonic peaks can be assigned immediately in the absorption-mode.

  2. Absorption-Mode Fourier Transform Mass Spectrometry: the Effects of Apodization and Phasing on Modified Protein Spectra

    PubMed Central

    Qi, Yulin; Li, Huilin; Wills, Rebecca H.; Perez-Hurtado, Pilar; Yu, Xiang; Kilgour, David. P. A.; Barrow, Mark P.; Lin, Cheng; O’Connor, Peter B.

    2014-01-01

    The method of phasing broadband FT-ICR spectra allows plotting the spectra in the absorption-mode; this new approach significantly improves the quality of the data at no extra cost. Herein, an internal calibration method for calculating the phase function has been developed, and successfully applied to the top-down spectra of modified proteins, where the peak intensities vary by >100×. The result shows that the use of absorption-mode spectra allows more peaks to be discerned within the recorded data, and this can reveal much greater information about the protein and modifications under investigation. In addition, noise and harmonic peaks can be assigned immediately in the absorption-mode. PMID:23568027

  3. Polarized electronic absorption spectra of Cr2SiO4 single crystals

    NASA Astrophysics Data System (ADS)

    Furche, A.; Langer, K.

    Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000-5000 cm-1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75 Å along [001]. The spectra were scanned at 273 and 120 K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6 μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20 μm and 1 nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35 kbar, above 1440 °C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm-1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10 Dq =10700 cm-1. A relatively intense, sharp band at 18400 cm-1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000 cm-1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr24+, whereas the latter alone would be in conflict with the strong

  4. Optical absorption spectra and energy levels of Er3+ ions in glassy lithium tetraborate matrix

    NASA Astrophysics Data System (ADS)

    Danilyuk, P. S.; Popovich, K. P.; Puga, P. P.; Gomonai, A. I.; Primak, N. V.; Krasilinets, V. N.; Turok, I. I.; Puga, G. D.; Rizak, V. M.

    2014-11-01

    The optical absorption spectra of Er:Li2B4O7 glasses are studied in the range 200-800 nm. The lines corresponding to the direct f-f parity-forbidden intraconfigurational transitions from the ground 4 I 15/2 state to the levels of the excited 4 F 9/2, 4 S 3/2, 2 H 9/2, 2 H 11/2, 4 F 7/2, 4 F 5/2, 4 F 3/2, 2 H 9/2, 4 G 11/2, 4 D 3/2, 4 D 1/2, and 2 D 3/2 states are found.

  5. Electrochromism in the near-infrared absorption spectra of bridged ruthenium mixed-valence complexes

    SciTech Connect

    Oh, D.H.; Boxer, S.G. )

    1990-10-24

    Many experimental and theoretical approaches have been developed to characterize the chemical and physical properties of mixed-valence complexes. These molecules may possess metals in differing oxidation states which participate in intervalence charge-transfer transitions. In principle, these transitions should be strongly affected by an external electric field. Such electrochromism can provide a direct and sensitive approach to investigating the electronic properties of molecules. The authors report the first measurements of the effects of an externally applied electric field on the near-infrared absorption spectra of ((NH{sub 3}){sub 5}Ru){sub 2}L{sup 5+} (L = pyrazine or 4,4{prime}-bipyridine). Significant differences are observed between the two complexes, illustrating the range of electronic interactions between the metal centers.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  7. Absorption and luminescence excitation spectra of ClF in the Vac UV region

    NASA Astrophysics Data System (ADS)

    Alekseev, Vadim A.; Schwentner, Nikolaus

    2010-07-01

    Absorption and luminescence excitation spectra of ClF are recorded in the vacuum ultraviolet employing synchrotron radiation. A broad band (120-130 nm) due to transition to the ion-pair state E(0 +) and sparse transitions to Rydberg states are observed. All Rydberg states are predissociated and their excitation yields no luminescence. Perturbations by the 4 sσ1Π 1 and 4p π1Σ + Rydberg states result in characteristic dips in the E(0 +) state luminescence excitation spectrum. Excitation above the Cl∗ + F dissociation threshold results in luminescence from ion-pair states of ClF or Cl 2 populated in reaction of Cl∗ with ClF or Cl 2.

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

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  10. Optical absorption and energy-loss spectra of aligned carbon nanotubes

    NASA Astrophysics Data System (ADS)

    García-Vidal, F. J.; Pitarke, J. M.

    2001-07-01

    Optical-absorption cross-sections and energy-loss spectra of aligned multishell carbon nanotubes are investigated, on the basis of photonic band-structure calculations. A local graphite-like dielectric tensor is assigned to every point of the tubules, and the effective transverse dielectric function of the composite is computed by solving Maxwell's equations in media with tensor-like dielectric functions. A Maxwell-Garnett-like approach appropriate to the case of infinitely long anisotropic tubules is also developed. Our full calculations indicate that the experimentally measured macroscopic dielectric function of carbon nanotube materials is the result of a strong electromagnetic coupling between the tubes. An analysis of the electric-field pattern associated with this coupling is presented, showing that in the close-packed regime the incident radiation excites a very localized tangential surface plasmon.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  13. Linewidth Extraction From the THz Absorption Spectra Using a Modified Lorentz Model

    NASA Astrophysics Data System (ADS)

    Li, Zhi; Zhang, Zhaohui; Zhao, Xiaoyan; Su, Haixia; Zhang, Han; Lan, Jinhui

    2013-10-01

    Identification of specific materials is one of the most promising THz applications. It is commonly achieved by comparing the experimental peak central frequencies of the transmission or absorption spectra with a database for known materials while neglecting the linewidths. However, due to the restriction of the signal-to-noise ratio, only a narrow band, extending from several hundred GHz to several THz, can be used. It is difficult to distinguish two materials from each other if their peaks' central frequencies are similar. In this paper, we present a modified Lorentz model by taking the scattering effect into account. The modified Lorentz model can be used for the extraction of reliable absorption peak parameters, i.e. the central frequency and linewidth. On comparison with our experiments, we observed that the parameters extracted using the modified Lorentz model in glutamine samples of different concentrations exhibited a better agreement than those obtained using the traditional model. Therefore, the utilization of the narrow THz band to identify materials can be improved by comparing both the central frequency and linewidth obtained from this method.

  14. Ab initio optical absorption spectra of size-expanded xDNA base assemblies.

    PubMed

    Varsano, Daniele; Garbesi, Anna; Di Felice, Rosa

    2007-12-20

    We present the results of time-dependent density functional theory calculations of the optical absorption spectra of synthetic nucleobases and of their hydrogen-bonded and stacked base pairs. We focus on size-expanded analogues of the natural nucleobases obtained through the insertion of a benzene ring bonded to the planar heterocycles (x-bases), according to the protocol designed and realized by the group of Eric Kool (e.g., see: Gao, J.; Liu, H.; Kool, E.T. Angew. Chem., Int. Ed. 2005, 44, 3118, and references therein). We find that the modifications of the frontier electron orbitals with respect to natural bases, which are induced by the presence of the aromatic ring, also affect the optical response. In particular, the absorption onset is pinned by the benzene component of the HOMO of each x-base (xA, xG, xT, xC). In addition, the main trait of the H-bonding interbase coupling is a conspicuous red shift of spectral peaks in the low-energy range. Finally, the hypochromicity, a well-known fingerprint of stacking, is more pronounced in stacked xG-C and xA-T pairs than that in stacked G-C and A-T pairs, an index of enhanced stacking. PMID:18034470

  15. The influence of thermolysis time on the absorption spectra of polyvinyl chloride in acetophenone

    NASA Astrophysics Data System (ADS)

    Rasmagin, S. I.; Krasovskii, V. I.; Vlasov, D. V.; Apresyan, L. A.; Vlasova, T. V.; Kryshtoba, V. I.; Feofanov, I. N.; Kazaryan, M. A.

    2015-12-01

    The influence of thermolysis time on the absorption spectra of partially thermally dehydrochlorinated polyvinyl chloride in acetophenone solution is studied. Strong increase in the optical density Dλ of the dehydrochlorinated PVC samples is caused by the increasing amount N-C=C- and the length of chains of conjugated double bonds of carbon -C = C-. It is noted that the optical density Dλ first increases linearly with dehydrochlorination time and then reaches saturation. The estimation of amount of double conjugated carbon bonds in 1ml versus thermolysis time t is given, which varies between N-C=C- = 4.1017 - 7.4.1018 for t from 40 to 420 minutes. The effective capture cross section of a photon on conjugated double bonds of carbon for dehydrochlorinated PVC solution in acetophenone is estimated, which was about 10-17 cm2 . The analysis is done of the absorption curves «red» shift to longer wavelengths with growth of N-C=C- upon increase of thermolysis time. It is noted that the dependence of the optical density on the wavelength in this range is well described by a simple exponential function.

  16. Ultraviolet spectra of quenched carbonaceous composite derivatives: Comparison to the '217 nanometer' interstellar absorption feature

    NASA Technical Reports Server (NTRS)

    Sakata, Akira; Wada, Setsuko; Tokunaga, Alan T.; Narisawa, Takatoshi; Nakagawa, Hidehiro; Ono, Hiroshi

    1994-01-01

    QCCs (quenched carbonaceous composite) are amorphus carbonaceous material formed from a hydrocarbon plasma. We present the UV-visible spectra of 'filmy QCC; (obtained outside of the beam ejected from the hydrocarbon plasma) and 'dark QCC' (obtained very near to the beam) for comparison to the stellar extinction curve. When filmy QCC is heated to 500-700 C (thermally altered), the wavelength of the absorption maximum increases form 204 nm to 220-222 nm. The dark QCC has an absorption maximum at 217-222 nm. In addition, the thermally altered filmy QCC has a slope change at about 500 nm which resmbles that in the interstellar extinction curve. The resemblance of the extinction curve of the QCCs to that of the interstellar medium suggests that QCC derivatives may be representative of the type of interstellar material that produces the 217 nm interstellar medium feature. The peak extinction of the dark QCC is higher than the average interstellar extinction curve while that of the thermally altered filmy QCC is lower, so that a mixture of dark and thermally altered filmy QCC can match the peak extinction observed in the interstellar medium. It is shown from electron micrographs that most of the thermally altered flimy QCC is in the form of small grainy structure less than 4 nm in diameter. This shows that the structure unit causing the 217-222 nm feature in QCC is very small.

  17. Solvent effects on the resonance Raman and electronic absorption spectra of bacteriochlorophyll a cation radical

    SciTech Connect

    Misono, Yasuhito; Itoh, Koichi; Limanatara, Leenawaty; Koyama, Yasushi

    1996-02-08

    Resonance Raman and electronic absorption spectra of bacteriocholrophyll a cation radical (BChl a{sup .+}) were recorded in 14 different kinds of solvents. The frequency of the ring-breathing Raman band of BChl a{sup .+} was in the region of 1596-1599 cm{sup -1} in solvents forming the pentacoordinated state in neutral bacteriochlorophyll a (BChl a), while it was in the region of 1584-1588 cm{sup -1} in solvents forming the hexacoordinated state. BChl a{sup .+} exhibited a key absorption band in the regions 546-554 and 557-563 nm in the above penta- and hexa-coordinating solvents. Therefore, it has been concluded that the penta- and hexa-coordinated states are retained even after conversion of BChl a into BChl a{sup .+} (one-electron oxidization). Application of this rule to the case of 2-propanol solution showed transformation from the penta- to the hexa-coordinated state upon one-electron oxidation in this particular solution. The coordination states of BChl a{sup .+} could be correlated with the donor number(DN) and the Taft parameters, {Beta} and {pi}{sup *}, of the solvent: The hexacoordinated state was formed in solvents with DN >= 18 or {Beta} > 0.5 showing higher electron donating power, while the pentacoordinated state was formed in solvents with {pi}{sup *} > 0.65 showing higher dielectric stabilization. 27 refs., 8 figs., 3 tabs.

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

    NASA Astrophysics Data System (ADS)

    Aydarous, Abdulkadir

    2016-05-01

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

  19. 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.

  20. Polarized absorption spectra of single crystals of lunar pyroxenes and olivines.

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Huggins, F. E.; Abu-Eid, R. M.

    1972-01-01

    Measurements have been made of the polarized absorption spectra (360-2200 nm) of compositionally zoned pyroxene minerals in rocks 10045, 10047 and 10058 and olivines in rocks 10020 and 10022. The Apollo 11 pyroxenes with relatively high Ti/Fe ratios were chosen initially to investigate the presence of crystal field spectra of Fe(2+) and Ti(3+) ions in the minerals. Broad intense bands at about 1000 and 2100 nm arise from spin-allowed, polarization-dependent transitions in Fe(2+) ions in pyroxenes. Several weak sharp peaks occur in the visible region. Peaks at 402, 425, 505, 550, and 585 nm represent spin-forbidden transitions in Fe(2+) ions, while broader bands at 460-470 nm and 650-660 nm are attributed to Ti(3+) ions. Charge transfer bands, which in terrestrial pyroxenes often extend into the visible region, are displaced to shorter wavelengths in lunar pyroxenes. This feature correlates with the absence of Ti(3+) ions in these minerals.

  1. Synthetic Spectra of H Balmer and HE I Absorption Lines. I. Stellar Library

    NASA Astrophysics Data System (ADS)

    González Delgado, Rosa M.; Leitherer, Claus

    1999-12-01

    We present a grid of synthetic profiles of stellar H Balmer and He I lines at optical wavelengths with a sampling of 0.3 Å. The grid spans a range of effective temperature 50,000 K>=Teff>=4000 K, and gravity 0.0<=logg<=5.0 at solar metallicity. For Teff>=25,000 K, non-LTE stellar atmosphere models are computed using the code TLUSTY (Hubeny). For cooler stars, Kurucz LTE models are used to compute the synthetic spectra. The grid includes the profiles of the high-order hydrogen Balmer series and He I lines for effective temperatures and gravities that have not been previously synthesized. The behavior of H8 to H13 and He I λ3819 with effective temperature and gravity is very similar to that of the lower terms of the series (e.g., Hβ) and the other He I lines at longer wavelengths; therefore, they are suited for the determination of the atmospheric parameters of stars. These lines are potentially important to make predictions for these stellar absorption features in galaxies with active star formation. Evolutionary synthesis models of these lines for starburst and poststarburst galaxies are presented in a companion paper. The full set of the synthetic stellar spectra is available for retrieval at our website or on request from the authors.

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

    NASA Astrophysics Data System (ADS)

    Porta, A.; Zakari-Issoufou, A.-A.; Fallot, M.; Algora, A.; Tain, J. L.; Valencia, E.; Rice, S.; Bui, V. M.; Cormon, S.; Estienne, M.; Agramunt, J.; Äystö, J.; Bowry, M.; Briz, J. A.; Caballero-Folch, R.; Cano-Ott, D.; Cucouanes, A.; Elomaa, V.-V.; Eronen, T.; Estévez, E.; Farrelly, G. F.; Garcia, A. R.; Gelletly, W.; Gomez-Hornillos, M. B.; Gorlychev, V.; Hakala, J.; Jokinen, A.; Jordan, M. D.; Kankainen, A.; Karvonen, P.; Kolhinen, V. S.; Kondev, F. G.; Martinez, T.; Mendoza, E.; Molina, F.; Moore, I.; Perez-Cerdán, A. B.; Podolyák, Zs.; Penttilä, H.; Regan, P. H.; Reponen, M.; Rissanen, J.; Rubio, B.; Shiba, T.; Sonzogni, A. A.; Weber, C.

    2016-03-01

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

  3. Deconvolution of C-phycocyanin beta-84 and beta-155 chromophore absorption and fluorescence spectra of cyanobacterium Mastigocladus laminosus.

    PubMed Central

    Demidov, A A; Mimuro, M

    1995-01-01

    Absorption and fluorescence spectra of the C-phycocyanin beta-subunit were quantitatively deconvoluted into component spectra of the beta-84 and beta-155 chromophores. The deconvolution procedure was based on a theoretical treatment of polarization properties. Four kinds of spectra (absorption, emission, emission polarization, and excitation polarization) measured on C-phycocyanin isolated from the cyanobacterium Mastigocladus laminosus were used as the experimental data set. Without any assumption of spectral shape, the absorption and fluorescence spectra of both chromophores were unambiguously resolved and their fluorescence quantum yields were evaluated. By combining the spectra of the alpha-subunit, independently measured, with the resolved spectra of the beta-subunit, the fluorescence and fluorescence polarization spectra and the fluorescence quantum yield of the monomer were estimated; they agree with experimental values to within an acceptable error. Further, the matrix of energy transfer rates in the monomer was estimated; it gave a significantly different result (by up to 40%) from previously estimated ones. PMID:7787035

  4. Absorption spectra and photolysis of methyl peroxide in liquid and frozen water.

    PubMed

    Epstein, Scott A; Shemesh, Dorit; Tran, Van T; Nizkorodov, Sergey A; Gerber, R Benny

    2012-06-21

    Methyl peroxide (CH(3)OOH) is commonly found in atmospheric waters and ices in significant concentrations. It is the simplest organic peroxide and an important precursor to hydroxyl radical. Many studies have examined the photochemical behavior of gaseous CH(3)OOH; however, the photochemistry of liquid and frozen water solutions is poorly understood. We present a series of experiments and theoretical calculations designed to elucidate the photochemical behavior of CH(3)OOH dissolved in liquid water and ice over a range of temperatures. The molar extinction coefficients of aqueous CH(3)OOH are different from the gas phase, and they do not change upon freezing. Between -12 and 43 °C, the quantum yield of CH(3)OOH photolysis is described by the following equation: Φ(T) = exp((-2175 ± 448)1/T) + 7.66 ± 1.56). We use on-the-fly ab initio molecular dynamics simulations to model structures and absorption spectra of a bare CH(3)OOH molecule and a CH(3)OOH molecule immersed inside 20 water molecules at 50, 200, and 220 K. The simulations predict large sensitivity in the absorption spectrum of CH(3)OOH to temperature, with the spectrum narrowing and shifting to the blue under cryogenic conditions because of constrained dihedral motion around the O-O bond. The shift in the absorption spectrum is not observed in the experiment when the CH(3)OOH solution is frozen suggesting that CH(3)OOH remains in a liquid layer between the ice grains. Using the extinction coefficients and photolysis quantum yields obtained in this work, we show that under conditions with low temperatures, in the presence of clouds with a high liquid-water content and large solar zenith angles, the loss of CH(3)OOH by aqueous photolysis is responsible for up to 20% of the total loss of CH(3)OOH due to photolysis. Gas phase photolysis of CH(3)OOH dominates under all other conditions. PMID:22217262

  5. Absorption spectra of isomeric OH adducts of 1,3,7-trimethylxanthine

    SciTech Connect

    Vinchurkar, M.S.; Rao, B.S.M.; Mohan, H.; Mittal, J.P.; Schmidt, K.H.; Jonah, C.D.

    1997-04-17

    The reactions of OH{sup .}, O{sup .-}, and SO{sub 4}{sup .-} with 1,3,7-trimethylxanthine (caffeine) were studied by pulse radiolysis with optical and conductance detection techniques. The absorption spectra of transients formed in OH{sup .} reaction in neutral solutions exhibited peaks at 310 and 335 nm, as well as a broad absorption maximum at 500 nm, which decayed by first-order kinetics. The rate (k = (4.0 {+-} 0.5) x 10{sup 4} s{sup -1}) of this decay is independent of pH in the range 4-9 and is in agreement with that determined from the conductance detection (k = 4 x 10{sup 4} s{sup -1}). The spectrum in acidic solutions has only a broad peak around 330 nm with no absorption in the higher wavelength region. The intermediates formed in reaction of O{sup .-} absorb around 310 and at 350 nm, and the first-order decay at the latter wavelength was not seen. The OH radical adds to C-4 (X-40H{sup .}) and C-8 (X-80H{sup .}) positions of caffeine in the ratio 1:2 as determined from the redox titration and conductivity measurements. H abstraction from the methyl group is an additional reaction channel in O{sup .-} reaction. Dehydroxylation of the X-40H{sup .} adduct occurs, whereas the X-80H{sup .} adduct does not undergo ring opening. The spectrum obtained for OH{sup .} reaction in oxygenated solutions is similar to that observed in SO{sub 4}{sup .-} reaction in basic solutions. 25 refs., 5 figs., 1 tab.

  6. O K-energy loss near-edge structure change induced by tantalum impurity in monoclinic hafnium oxide

    SciTech Connect

    Yang, Mino; Baik, Hionsuck; Ivanovskaya, Viktoria; Colliex, Christian; Benayad, Anass

    2011-03-01

    The present paper reports the energy loss near-edge structure (ELNES) study of monoclinic HfO{sub 2} (m-HfO{sub 2}) and tantalum doped m-HfO{sub 2} (Ta{sub 0.1}Hf{sub 0.9}O{sub 2}) thin films prepared by radio frequency magnetron co-sputtering method. A change in the O K-ELNES spectra was observed as the amount of dopant increases. In order to precise the common features and the differences as a function of Ta defect nature (substitutional or interstitial) in HfO{sub 2}, the O K-ELNES were commented with respect to density functional theory calculations implemented in Vienna ab initio simulation package code. The calculated Ta doped HfO{sub 2} band structure showed that substitutional tantalum is the dominant defect and the spectral differences between doped and non-doped HfO{sub 2} are mainly originated from the change in the local cation distribution around the oxygen atoms.

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

    PubMed

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

    2014-05-14

    Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σp and σm). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes. PMID:24801959

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

    PubMed

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

    2016-09-13

    The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption and the emission maximum in water are significantly blue-shifted (0.08 eV). The absorption spectra are simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with three different approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) a mixed QM/MM static approach, and (iii) a QM/MM method exploiting the structures issuing from molecular dynamics classical simulations. Ab-initio Molecular dynamics simulations based on CAM-B3LYP functionals have also been performed. The adopted approaches all reproduce the main features of the experimental spectra, giving insights on the chemical-physical effects responsible for the solvent shifts in the spectra of 5-methylcytidine and providing the basis for discussing advantages and limitations of the adopted solvation models. PMID:27529792

  9. First principle studies on the electronic structures and absorption spectra in KMgF 3 crystal with fluorine vacancy

    NASA Astrophysics Data System (ADS)

    Cheng, Fang; Liu, Tingyu; Zhang, Qiren; Qiao, Hailin; Zhou, Xiuwen

    2010-08-01

    The experiments indicate that the perfect KMgF 3 crystal has no absorption in the visible range, however the electron irradiation induces a complex absorption spectrum. The absorption spectra can be decomposed by five Gaussian bands peaking at 2.5 eV (488 nm), 3.4 eV (359 nm), 4.2 eV (295 nm), 4.6 eV (270 nm) and 5.2 eV (239 nm), respectively. The purpose of this paper is to seek the origins of the absorption bands. The electronic structures and absorption spectra either for the perfect KMgF 3 or for KMgF 3: VF+ with electrical neutrality have been studied by using density functional theory code CASTEP with the lattice structure optimized. The calculation results predicate that KMgF 3: VF+ also exhibits five absorption bands caused by the existence of the fluorine ion vacancy VF+ and the five absorption bands well coincide with the experimental results. It is believable that the five absorption bands are related to VF+ in KMgF 3 crystal produced by the electron irradiation.

  10. Optical Absorption Spectra and Excitons of Dye-Substrate Interfaces: Catechol on TiO2(110).

    PubMed

    Mowbray, Duncan John; Migani, Annapaola

    2016-06-14

    Optimizing the photovoltaic efficiency of dye-sensitized solar cells (DSSC) based on staggered gap heterojunctions requires a detailed understanding of sub-band gap transitions in the visible from the dye directly to the substrate's conduction band (CB) (type-II DSSCs). Here, we calculate the optical absorption spectra and spatial distribution of bright excitons in the visible region for a prototypical DSSC, catechol on rutile TiO2(110), as a function of coverage and deprotonation of the OH anchoring groups. This is accomplished by solving the Bethe-Salpeter equation (BSE) based on hybrid range-separated exchange and correlation functional (HSE06) density functional theory (DFT) calculations. Such a treatment is necessary to accurately describe the interfacial level alignment and the weakly bound charge transfer transitions that are the dominant absorption mechanism in type-II DSSCs. Our HSE06 BSE spectra agree semiquantitatively with spectra measured for catechol on anatase TiO2 nanoparticles. Our results suggest deprotonation of catechol's OH anchoring groups, while being nearly isoenergetic at high coverages, shifts the onset of the absorption spectra to lower energies, with a concomitant increase in photovoltaic efficiency. Further, the most relevant bright excitons in the visible region are rather intense charge transfer transitions with the electron and hole spatially separated in both the [110] and [001] directions. Such detailed information on the absorption spectra and excitons is only accessible via periodic models of the combined dye-substrate interface. PMID:27183273

  11. The D2O absorption spectra in SiO2 airgel pores: technical features of treatment

    NASA Astrophysics Data System (ADS)

    Lugovskoi, A.; Duchko, A.

    2015-11-01

    The dynamic of the D2O in silica airgel absorption spectra in 4000…6000 cm-1 were recorded using Fourier Transform spectrometer FS-125M at room temperature and pressure of 23.4 mbar with spectral resolution of 0.03 cm-1. It is shown that the D2O dimers to make a significant contribution into absorption when nanopores filled with gas molecules is small. Is present a detailed description of techniques for processing the primary experimental data.

  12. The determination of absorption cross sections and line profiles in vibrational overtone spectra with the use of intracavity absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Bettermann, H.; Kleist, E.; Kok, R.

    1993-03-01

    This contribution presents quantitative absorption data concerning the 7 th CH overtone stretching vibrations of n-hexane and of methylcyclopentane. The transitions are adapted to Lorentzian and Gaussian line shapes. The bank shape analyses yield the spectral positions, absorption cross sections and linewidths of the investigated transitions.

  13. Detection of water vapour absorption around 363nm in measured atmospheric absorption spectra and its effect on DOAS evaluations

    NASA Astrophysics Data System (ADS)

    Lampel, Johannes; Polyansky, Oleg. L.; Kyuberis, Alexandra A.; Zobov, Nikolai F.; Tennyson, Jonathan; Lodi, Lorenzo; Pöhler, Denis; Frieß, Udo; Platt, Ulrich; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Water vapour is known to absorb light from the microwave region to the blue part of the visible spectrum at a decreasing magnitude. Ab-initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines until its dissociation limit at 243 nm. We present first evidence of water vapour absorption at 363 nm from field measurements based on the POKAZATEL absorption line list by Polyansky et al. (2016) using data from Multi-Axis differential optical absorption spectroscopy (MAX-DOAS) and Longpath (LP)-DOAS measurements. The predicted absorptions contribute significantly to the observed optical depths with up to 2 × 10‑3. Their magnitude correlates well (R2 = 0.89) to simultaneously measured well-established water vapour absorptions in the blue spectral range from 452-499 nm, but is underestimated by a factor of 2.6 ± 0.6 in the ab-initio model. At a spectral resolution of 0.5nm this leads to a maximum absorption cross-section value of 5.4 × 10‑27 cm2/molec at 362.3nm. The results are independent of the employed cross-section data to compensate for the overlayed absorption of the oxygen dimer O4. The newly found absorption can have a significant impact on the spectral retrieval of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO are discussed.

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

    SciTech Connect

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

    2010-03-11

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

  15. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... by both molar absorption coefficient (molar extinction coefficient) and band width. However, the..., expressed in cm; and the molar absorption (extinction) coefficient,εi, of each species. The...

  16. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... by both molar absorption coefficient (molar extinction coefficient) and band width. However, the..., expressed in cm; and the molar absorption (extinction) coefficient,εi, of each species. The...

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... by both molar absorption coefficient (molar extinction coefficient) and band width. However, the..., expressed in cm; and the molar absorption (extinction) coefficient,εi, of each species. The...

  18. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... by both molar absorption coefficient (molar extinction coefficient) and band width. However, the..., expressed in cm; and the molar absorption (extinction) coefficient,εi, of each species. The...

  19. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... by both molar absorption coefficient (molar extinction coefficient) and band width. However, the..., expressed in cm; and the molar absorption (extinction) coefficient,εi, of each species. The...

  20. High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

    NASA Astrophysics Data System (ADS)

    Sonneborn, G.; Iping, R. C.; Gull, T. R.; Vieira, G.

    2002-12-01

    Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127-22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg II, Fe II, V II, etc observed in STIS/E230H spectra (see accompanying posters by Gull, Vieira, and Danks). The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-1 above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30x30 arcsec for FUSE, 0.2x0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic miniumum in 2003.

  1. High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

    NASA Technical Reports Server (NTRS)

    Sonneborn, G.; Iping, R. C.; Gull, T. R.; Vieira, G.

    2003-01-01

    Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127- 22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg 11, Fe II, V II, etc observed in STIS/E230H spectra. The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-l above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30 x 30 arcsec for FUSE, 0.2 x 0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic minimum in 2003.

  2. Wavelet based de-noising of breath air absorption spectra profiles for improved classification by principal component analysis

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    The comparison results of different mother wavelets used for de-noising of model and experimental data which were presented by profiles of absorption spectra of exhaled air are presented. The impact of wavelets de-noising on classification quality made by principal component analysis are also discussed.

  3. 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.

  4. Gravitationally redshifted absorption lines in the X-ray burst spectra of a neutron star.

    PubMed

    Cottam, J; Paerels, F; Mendez, M

    2002-11-01

    The fundamental properties of neutron stars provide a direct test of the equation of state of cold nuclear matter, a relationship between pressure and density that is determined by the physics of the strong interactions between the particles that constitute the star. The most straightforward method of determining these properties is by measuring the gravitational redshift of spectral lines produced in the neutron star photosphere. The equation of state implies a mass-radius relation, while a measurement of the gravitational redshift at the surface of a neutron star provides a direct constraint on the mass-to-radius ratio. Here we report the discovery of significant absorption lines in the spectra of 28 bursts of the low-mass X-ray binary EXO0748-676. We identify the most significant features with the Fe XXVI and XXV n = 2-3 and O VIII n = 1-2 transitions, all with a redshift of z = 0.35, identical within small uncertainties for the respective transitions. For an astrophysically plausible range of masses (M approximately 1.3-2.0 solar masses; refs 2-5), this value is completely consistent with models of neutron stars composed of normal nuclear matter, while it excludes some models in which the neutron stars are made of more exotic matter. PMID:12422210

  5. Novel Techniques and Approaches to Unravel the Nature of X-Ray Absorption Spectra

    SciTech Connect

    Groot, F. M. F. de

    2007-02-02

    This paper discusses the role of resonant inelastic X-ray scattering (RIXS) to unravel the nature of the states that are visible in the pre-edge region of the 3d metal K edges. The traditional pre-edge analysis into quadrupole transitions to the 3d-states plus dipole transitions to the 4p states is outlined, with special attention to the situation of TiO2. The general possibilities of RIXS are described, including the various possible cross-sections through the 2D RIXS plane. Recent developments in High-Energy Resolution Fluorescence Detection (HERFD) are discussed, that yield XANES-like spectra with unprecedented resolution. Using the 1s2p RIXS of LiCoO2 as example, the presence of an extra peak due to non-local dipole transitions is explained. The non-local nature of this dipole pre-edge peak is proven from its behavior in the 2D RIXS plane. The paper also discusses a range of selective X-ray absorption experiments, where the selectivity is towards (a) the spin-state, (b) the valence, (c) the neighbor atom and (d) the edge. In the outlook, a number of additional experimental routes is suggested, which shows that the use of RIXS, HERFD and selective XAS techniques is only just starting.

  6. Strong anisotropy in the THz absorption spectra of stretch-aligned single walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Iwasa, Y.; Akima, N.; Matsui, H.; Toyota, N.; Brown, S.; Barbour, A. M.; Cao, J.; Musfeldt, J. L.; Shiraishi, M.; Shimoda, H.; Zhou, O.

    2006-03-01

    Polarized THz spectroscopy is crucial for understanding the low-energy electronic structure and carrier dynamics in single walled carbon nanotubes (SWNTs), as well as for exploring polarization-sensitive THz applications. We prepared stretch-aligned SWNT/polymer composites, and measured the polarized absorption spectra from the THz through the visible region. The low-frequency electronic excitations are predominantly polarized parallel to the tube direction. The peak centered near 100 cm-1 is discussed in terms of a curvature-induced gap and a plasmon resonance due to a finite size/wavelength effects in the SWNTs. The broad middle infrared structure that is observed in unoriented films with spaghetti-like morphology disappears in stretch-aligned samples, suggesting that this middle infrared feature may be due to in-gap states in the semiconducting tubes caused by the highly disordered morphology of the unoriented films. Hole doping effects were also investigated, and conversion of semiconducting tubes to more conducting ones is demonstrated.

  7. Absorption spectra and sunlight conversion efficiency in fullerene bonded supramolecules on nanostructured ZnO

    NASA Astrophysics Data System (ADS)

    Zakhidov, Erkin; Kokhkharov, Abdumutallib; Kuvondikov, Vakhobjon; Nematov, Sherzod; Nusretov, Rafael

    2015-10-01

    The efficiency of solar radiation conversion in a model system of artificial photosynthesis, the porphyrin-fullerene assembly, is analyzed. A study of the optical absorption spectra of the porphyrin and the fullerene molecules, as well as their assembly in organic solutions, made it possible to estimate the energy efficiency of the conversion. Numerical values of the energy efficiency, defined as the fraction of the light quantum energy converted to the chemical potential of separated charges, are calculated for low- and high-concentration solutions of such a supramolecular system. The possibility of the efficient utilization of long-wavelength solar radiation in the high-concentration porphyrin-fullerene assembly solution in toluene and benzene is shown. In the photovoltaic system consisting of such a supramolecular active element, a thin ZnO film with a nanostructured surface may be introduced as a secondary acceptor of electrons from fullerene molecules. An enhancement of the transformation of separated charges of the porphyrin-fullerene assembly into electrical current by means of the ZnO film deposited on the surface of the anode electrode in such a heterogenic photovoltaic unit is proposed.

  8. Bethe-Salpeter calculation of optical-absorption spectra of In2O3 and Ga2O3

    NASA Astrophysics Data System (ADS)

    Varley, Joel B.; Schleife, André

    2015-02-01

    Transparent conducting oxides keep attracting strong scientific interest not only due to their promising potential for ‘transparent electronics’ applications but also due to their intriguing optical absorption characteristics. Materials such as In2O3 and Ga2O3 have complicated unit cells and, consequently, are interesting systems for studying the physics of excitons and anisotropy of optical absorption. Since currently no experimental data is available, for instance, for their dielectric functions across a large photon-energy range, we employ modern first-principles computational approaches based on many-body perturbation theory to provide theoretical-spectroscopy results. Using the Bethe-Salpeter framework, we compute dielectric functions and we compare to spectra computed without excitonic effects. We find that the electron-hole interaction strongly modifies the spectra and we discuss the anisotropy of optical absorption that we find for Ga2O3 in relation to existing theoretical and experimental data.

  9. Vibrationally Resolved Absorption and Fluorescence Spectra of Firefly Luciferin: A Theoretical Simulation in the Gas Phase and in Solution.

    PubMed

    Cheng, Yuan-Yuan; Liu, Ya-Jun

    2016-07-01

    Firefly bioluminescence has been applied in several fields. However, the absorption and fluorescence spectra of the substrate, luciferin, have not been observed at the vibrational level. In this study, the vibrationally resolved absorption and fluorescence spectra of firefly luciferin (neutral form LH2 , phenolate ion form LH(-) and dianion form L(2-) ) are simulated using the density functional method and convoluted by a Gaussian function, with displacement, distortion and Duschinsky effects in the framework of the Franck-Condon approximation. Both neutral and anionic forms of the luciferin are considered in the gas phase and in solution. The simulated spectra have desired band maxima with the experimental ones. The vibronic structure analysis reveals that the features of the most contributive vibrational modes coincide with the key geometry-changing region during transition between the ground state and the first singlet excited state. PMID:27165852

  10. Identifying student and teacher difficulties in interpreting atomic spectra using a quantum model of emission and absorption of radiation

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    Our study sets out to identify the difficulties that high school students, teachers, and university students encounter when trying to explain atomic spectra. To do so, we identify the key concepts that any quantum model for the emission and absorption of electromagnetic radiation must include to account for the gas spectra and we then design two questionnaires, one for teachers and the other for students. By analyzing the responses, we conclude that (i) teachers lack a quantum model for the emission and absorption of electromagnetic radiation capable of explaining the spectra, (ii) teachers and students share the same difficulties, and (iii) these difficulties concern the model of the atom, the model of radiation, and the model of the interaction between them.

  11. Electronic absorption spectra of U3+ and U4+ in molten LiCl-RbCl eutectic

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    In the non-aqueous reprocessing process of spent nuclear fuels by the pyro-electrochemical method, a spent fuel is dissolved into molten LiCl-KCl and NaCl-CsCl eutectics and dissolved uranium and plutonium are collected as either metal or oxide. However, the binary alkali chloride mixture with the lowest melting point is the LiCl-RbCl eutectic. In this study, electronic absorption spectra of U3+ and U4+ in molten LiCl-RbCl eutectic at various temperatures between 673 and 973 K were measured by the UV/Vis/NIR spectrophotometry. We confirmed that these spectra were similar to those in molten LiCl-KCl and NaCl-CsCl eutectics. The sensitive absorption bands of U4+ in LiCl-RbCl eutectic were found at 22000, 16500, 14900, 8600, and 4950 cm-1. The large absorption bands of U4+ over 25000 cm-1 increased with increasing melt temperature, while absorption peaks at 15500-4000 cm-1 decreased. The large absorption bands of U3+ in LiCl-RbCl eutectic were observed over 14000 cm-1. The sensitive absorption bands of U3+ at Vis/NIR region were found at 13300, 11500-11200, 9800-9400, and 8250 cm-1, and these peaks decreased with increasing temperature.

  12. Analysis of Gain and Absorption Spectra of Gallium Nitride-based Laser Diodes

    NASA Astrophysics Data System (ADS)

    Melo, Thiago

    Laser diodes (LDs) based on the III-Nitride material system, (Al,In,Ga)N, stand to satisfy a number of application needs, and their huge market segment has been further growing with the use of LDs for full color laser projection. All commercially available GaN-based devices are based on the conventional c-plane (polar) orientation of this material. However, strong polarization fields caused by strained quantum-well (QW) layers on c-plane induce the quantum-confined Stark effect (QCSE), which leads to reduced radiative recombination rate and are aggravated when more indium is added into the QW(s) in order to achieve longer wavelengths. A promising solution for this is the use of nonpolar and semipolar crystal growth orientations. Elimination or mitigation of polarization-related fields within the QWs grown along these novel orientations is observed and one expects increased radiative recombination rate and stabilization of the wavelength emission with respect to the injection current. In order to have more insights on the advantages of using the novel crystal orientations of the III-Nitride material system, we compare the gain of LD structures fabricated from c-plane, nonpolar and semipolar GaN substrates. Using thesegmented contact method, single-pass gain spectra of LD epitaxial structures at wafer level are compared for the different crystal orientations as well as the single-pass absorption coefficient spectrum of the active region material and its dependence on reversed bias. Experimental gain spectra under continuous-wave (CW) operation of actual industry LDs fabricated from c-plane and nonpolar/semipolar GaN-based materials emitting wavelengths in the visible are then presented, using the Hakki-Paoli technique at high resolution. Measurements of the transparency current density, total losses and differential modal gain curves up to threshold are analyzed and compared between nonpolar/semipolar and c-plane LDs in violet and blue spectral regions regions. In a

  13. Computational study of collision-induced dipole moments and absorption spectra of H

    NASA Astrophysics Data System (ADS)

    Zheng, Chunguang

    1997-08-01

    H2-H2 collision-induced absorption (CIA) spectra are computed for the first over-tone band at temperatures from 20 to 500 K, and for the rototranslational band at temperatures from 600 to 7,000 K. The theoretical results are based on simple model line shapes. The parameters of the model functions are obtained from the three lowest translational spectral moments, which are computed from the H2-H2 collision-induced dipole moments of Meyer et al. (1) using the sum formulae (2, 3). Ab initio computations of H2-H2 collision- induced dipole moments are performed using the Gaussian 92 program (4). The computations extend the previous work of Meyer et al. (1). Four internuclear distances of H2 molecule 1.111, 1.449, 1.787 and 2.150 a.u., and eleven intermolecular distances of H2-H2 from 2.5 to 9.0 a.u. are included in the computations. The radial transition matrix elements of the collision- induced dipole components are obtained for vibrational transitions /Delta v = (v1' - v1) + (v2' - v2) = 0, 1, 2, 3 and v1,/ v2 = 0, 1, 2. where v1 and v2 are the vibrational quantum numbers of the two interacting H2 molecules, and primes denote final states. The dependences of these matrix elements on the rotational quantum numbers of the two H2 molecules j1j1'j2j2' are obtained for j1j1'j2j2' up to 10. These matrix elements are suitable for high temperature H2-H2 CIA computations. The second overtone band H2-H2 CIA spectra are computed for the first time at temperatures from 20 to 500 K employing the newly developed H2-H2 collision-induced dipole moments. The computations are based on the three lowest translational spectral moments and simple model line shapes.

  14. Analysis of Atmospheric Trace Constituents from High Resolution Infrared Balloon-Borne and Ground-Based Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Rinsland, C. P.; Blatherwick, R. D.; Murcray, F. H.; Murcray, D. G.

    1991-01-01

    Recent results and ongoing studies of high resolution solar absorption spectra will be presented. The analysis of these spectra is aimed at the identification and quantification of trace constituents important in atmospheric chemistry of the stratosphere and upper troposphere. Analysis of balloon-borne and ground-based spectra obtained at 0.0025/ cm covering the 700-2200/ cm interval will be presented. Results from ground-based 0.02/ cm solar spectra, from several locations such as Denver, South Pole, M. Loa, and New Zealand will also be shown. The 0.0025/ cm spectra show many new spectroscopic features. The analysis of these spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of trace constituents quantification. The combination of the recent balloon flights, with earlier flights data since 1978 at 0.02/ cm resolution, provides trends analysis of several stratospheric trace species. Results for COF2, F22, SF6, and other species will be presented. Analysis of several ground-based solar spectra provides trends for HCl, HF and other species. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra will be presented. These are extended for the analysis of the ground-based spectra to be obtained by the high resolution interferometers of the Network for Detection of Stratospheric Change (NDSC). Progress or the University of Denver studies for the NDSC will be presented. This will include intercomparison of solar spectra and trace gases retrievals obtained from simultaneous scans by the high resolution (0.0025/ cm) interferometers of BRUKER and BOMEM.

  15. Photodynamic cancer therapy: fluorescence localization and light absorption spectra of chlorophyll-derived photosensitizers inside cancer cells

    NASA Astrophysics Data System (ADS)

    Moser, Joerg G.; Rueck, Angelika C.; Schwarzmaier, Hans-Joachim; Westphal-Frosch, Christel

    1992-07-01

    The first prerequisite for an optimum effect of photodynamic therapy with chlorophyll- derived photosensitizers is irradiation at the S1 absorption maximum in the red spectral region. This absorption maximum changes its position due to molecular association by 20 to 100 nm depending on the subcellular environment, and must be determined by direct absorption spectrometry in the region of subcellular sensitizer localization. Fluorescence- intensifying video microscopy allows for localization of the sensitizer storage site at or near the Galgi apparatus of OAT 75 small-cell lung carcinoma cells. The absorption maximum at 760 nm taken from spectra of single cells and cell layers determines the postulated optimum condition for dye laser irradiation with bacteriopheophorbide-a-methyl-ester as the sensitizer.

  16. Solvent dependence of two-photon absorption spectra of the enhanced green fluorescent protein (eGFP) chromophore

    NASA Astrophysics Data System (ADS)

    Hosoi, Haruko; Tayama, Ryo; Takeuchi, Satoshi; Tahara, Tahei

    2015-06-01

    Two-photon absorption spectra of 4‧-hydroxybenzylidene-2,3-dimethylimidazolinone, a model chromophore of enhanced green fluorescent protein (eGFP), were measured in various solvents. The two-photon absorption band of its anionic form is markedly blue-shifted from the corresponding one-photon absorption band in all solvents. Moreover, the magnitude of the blue shift varies largely depending on the solvent, which does not accord with the assignment of the two-photon absorption band to the transitions to the vibrationally excited S1 state. Our finding is readily rationalized by considering overlapping contributions of the S1 ← S0 and S2 ← S0 transitions, suggesting the involvement of the S2 state also in two-photon fluorescence of eGFP.

  17. Absorption spectra of CdSe-ZnS core-shell quantum dots at high photon energies: Experiment and modeling

    NASA Astrophysics Data System (ADS)

    Mukherjee, Amlan; Ghosh, Sandip

    2014-11-01

    Absorption spectra of CdSe-ZnS core-shell quantum dot (QD) ensembles, with average core diameters ranging from 2.6 nm to 7.2 nm have been obtained using both transmission and photoluminescence excitation measurements. In agreement with previous reports, the absorption coefficient at energies ≃1 eV above the effective bandgap increases monotonically as in bulk solids. A simple effective-mass spherical core-shell potential model cannot explain the relatively high absorption at higher energies. The calculated electron and hole radial envelope wavefunctions show asymmetry due to the core-shell structure. It leads to normally symmetry-disallowed transitions acquiring a weak oscillator strength, with their number and strength increasing with energy. A phenomenological model that invokes normally disallowed transitions in general is shown to reproduce the absorption spectrum at higher energies quite well. The oscillator strength scaling factor for such transitions increases with decrease in QD size, consistent with expectations.

  18. Collison-induced rototranslational absorption spectra of H/sub 2/-He pairs at temperatures from 40 to 3000 K

    SciTech Connect

    Borysow, J.; Frommhold, L.; Birnbaum, G.

    1988-03-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H/sub 2/-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K. 28 references.

  19. On-the-Fly ab Initio Semiclassical Dynamics of Floppy Molecules: Absorption and Photoelectron Spectra of Ammonia.

    PubMed

    Wehrle, Marius; Oberli, Solène; Vaníček, Jiří

    2015-06-01

    We investigate the performance of on-the-fly ab initio (OTF-AI) semiclassical dynamics combined with the thawed Gaussian approximation (TGA) for computing vibrationally resolved absorption and photoelectron spectra. Ammonia is used as a prototype of floppy molecules, whose potential energy surfaces display strong anharmonicity. We show that despite complications due to the presence of large amplitude motion, the main features of the spectra are captured by the OTF-AI-TGA, which—by definition—does not require any a priori knowledge of the potential energy surface. Moreover, the computed spectra are significantly better than those based on the popular global harmonic approximation. Finally, we probe the limit of the TGA to describe higher-resolution spectra, where long time dynamics is required. PMID:25928833

  20. Collison-induced rototranslational absorption spectra of H2-He pairs at temperatures from 40 to 3000 K

    NASA Technical Reports Server (NTRS)

    Borysow, Jacek; Frommhold, Lothar; Birnbaum, George

    1988-01-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H2-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    It is very important to determine electron transition energies (Etr) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV-vis absorption spectra using the curve (αhν)2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV-vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (Etr) between the anions and cations, Fe2+ and Fe3+ at the (A) and [B] sites and Ni2+ at the [B] sites for the (A)[B]2O4 spinel ferrite samples CoxNi0.7-xFe2.3O4 (0.0≤x≤0.3), CrxNi0.7Fe2.3-xO4 (0.0≤x≤0.3) and Fe3O4. We suggest that the differential UV-vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  2. Interpretation of unexpected behavior of infrared absorption spectra of ScF3 beyond the quasiharmonic approximation

    NASA Astrophysics Data System (ADS)

    Piskunov, Sergei; Žguns, Pjotrs A.; Bocharov, Dmitry; Kuzmin, Alexei; Purans, Juris; Kalinko, Aleksandr; Evarestov, Robert A.; Ali, Shehab E.; Rocca, Francesco

    2016-06-01

    Scandium fluoride (ScF3), having cubic ReO3-type structure, has attracted much scientific attention due to its rather strong negative thermal expansion (NTE) in the broad temperature range from 10 to 1100 K. Here we use the results of diffraction and extended x-ray absorption fine-structure (EXAFS) spectroscopy to interpret the influence of NTE on the temperature dependence of infrared absorption spectra of ScF3. Original infrared absorption and EXAFS experiments in a large temperature range are presented and interpreted using ab initio lattice dynamics simulations within and beyond quasiharmonic approximations. We demonstrate that ab initio electronic structure calculations, based on the linear combination of atomic orbitals method with hybrid functionals, are able to reproduce well the experimental values of lattice parameter a0, band gap Eg, and lattice dynamics in ScF3. However, the simulations performed within quasiharmonic approximation fail to reproduce the temperature dependence of two infrared active bands due to the F-Sc-F bending (at 220 cm-1) and Sc-F stretching (at 520 cm-1) modes present in the infrared absorption spectra. To overcome this problem, an approach beyond the quasiharmonic approximation is proposed: It accounts for the negative thermal expansion of the lattice and for fluorine atom displacements due to strong F vibrational motion perpendicular to the cubic axes and allows us to explain qualitatively the temperature behavior of infrared spectra of ScF3.

  3. Electronic Absorption Spectra of Tetrapyrrole-Based Pigments via TD-DFT: A Reduced Orbital Space Study.

    PubMed

    Shrestha, Kushal; Virgil, Kyle A; Jakubikova, Elena

    2016-07-28

    Tetrapyrrole-based pigments play a crucial role in photosynthesis as principal light absorbers in light-harvesting chemical systems. As such, accurate theoretical descriptions of the electronic absorption spectra of these pigments will aid in the proper description and understanding of the overall photophysics of photosynthesis. In this work, time-dependent density functional theory (TD-DFT) at the CAM-B3LYP/6-31G* level of theory is employed to produce the theoretical absorption spectra of several tetrapyrrole-based pigments. However, the application of TD-DFT to large systems with several hundreds of atoms can become computationally prohibitive. Therefore, in this study, TD-DFT calculations with reduced orbital spaces (ROSs) that exclude portions of occupied and virtual orbitals are pursued as a viable, computationally cost-effective alternative to conventional TD-DFT calculations. The effects of reducing orbital space size on theoretical spectra are qualitatively and quantitatively described, and both conventional and ROS results are benchmarked against experimental absorption spectra of various tetrapyrrole-based pigments. The orbital reduction approach is also applied to a large natural pigment assembly that comprises the principal light-absorbing component of the reaction center in purple bacteria. Overall, we find that TD-DFT calculations with proper and judicious orbital space reductions can adequately reproduce conventional, full orbital space, TD-DFT results of all pigments studied in this work. PMID:27392135

  4. Interconfigurational absorption and two-photon excitation spectra of PtCl sub 6 sub 2 minus -containing crystals

    SciTech Connect

    Yoo, Ryong, K.; Keiderling, T.A. )

    1990-10-18

    Low-temperature absorption and two-photon excitation spectra of complexes containing PtCl{sub 6}{sup 2{minus}} are presented and discussed. One-photon absorption spectra with moderately well resolved vibronic structure were obtained for PtCl{sub 6}{sup 2{minus}} in dilute mixed crystals. The data show that a transition to a low-lying interconfigurational state is located at {approximately} 18,000 cm{sup {minus}1} in the spectral frequency region below the first absorption transition previously assigned by others. This transition cannot be unambiguously assigned. If it corresponds to the same excited state responsible for the PtCl{sub 6}{sup 2{minus}} emission spectrum, this would lead to a partial reassignment of the excited states from that of earlier work. Ligand field calculations consistent with such a reassignment are presented. The two-photon excitation (TPE) spectra of the mixed Cs{sub 2}ZrCl{sub 6}:PtCl{sub 6}{sup 2{minus}} and pure K{sub 2}PtCl{sub 6} (at 77 K), measured with an improved spectrometer, show a noticeable improvement in signal-to-noise ratio compared to the previously reported TPE spectra of K{sub 2}PtCl{sub 6} and are assigned to higher energy d-d transitions.

  5. Calculation of emission and absorption spectra of LTE plasma by the STA (Super Transition Array) method

    SciTech Connect

    Bar-Shalon, A.; Oreg, J. . Nuclear Research Center-Negev); Goldstein, W.H. )

    1991-01-11

    Recent improvements in the Super Transition Array (STA) method for calculating Bound-Bound (BB) and Bound-Free (BF) emission and absorption spectra for LTE plasma are described and illustrated. The method accounts for all possible BB and BF radiative transitions in the plasma. Full detailed first order quantum relativistic treatment is used for calculating transition energies and probabilities. The enormous number of configurations are divided into sets of superconfigurations comprised of a collection of energetically grouped configurations. The contribution of the transition array between two superconfigurations to a specific one-electron transition is then represented by a Gaussian whose moments are calculated accurately using a technique that bypasses the necessity of direct summation over all the levels involved. The calculation of these moments involves the populations of the configurations given by their statistical weights and the Boltzmann factor. For each configuration within the super configuration we use zeroeth order energies in the Boltzmann factor corrected by a super configuration averaged first order term. The structure of the spectrum is increasingly revealed by splitting each STA into a number of smaller STAs. When the spectrum converges it describes the detailed UTA' structure, where each configuration-to-configuration array is represented by a separate Gaussian with first order energy in the Boltzmann factor. Convergence is reached with only a few thousand STAs, at most, which makes the calculations practical. It should be pointed out that in this treatment the STA moments are obtained by summing over all level-to-level transitions, rather than configuration-to-configuration average transitions. 4 refs., 9 figs.

  6. Variability, absorption features, and parent body searches in "spectrally featureless" meteorite reflectance spectra: Case study - Tagish Lake

    NASA Astrophysics Data System (ADS)

    Izawa, M. R. M.; Craig, M. A.; Applin, D. M.; Sanchez, J. A.; Reddy, V.; Le Corre, L.; Mann, P.; Cloutis, E. A.

    2015-07-01

    Reflectance spectra of many asteroids and other Solar System bodies are commonly reported as "featureless". Here, we show that weak but consistently detectable absorption bands are observable in 200-2500 nm spectra of the Tagish Lake meteorite, a likely compositional and spectral analogue for low-albedo, "spectrally-featureless" asteroids. Tagish Lake presents a rare opportunity to study multiple lithologies within a single meteorite. Reflectance spectra of Tagish Lake display significant variation between different lithologies. The spectral variations are due in part to mineralogical variations between different Tagish Lake lithologies. Ultraviolet reflectance spectra (200-400 nm), few of which have been reported in the literature to date, reveal albedo and spectral ratio variations as a function of mineralogy. Similarly visible-near infrared reflectance spectra reveal variations in albedo, spectral slope, and the presence of weak absorption features that persist across different lithologies and can be attributed to various phases present in Tagish Lake. These observations demonstrate that significant spectral variability may exist between different lithologies of Tagish Lake, which may affect the interpretation of potential source body spectra. It is also important to consider the spectral variability within the meteorite before excluding compositional links between possible parent bodies in the main belt and Tagish Lake. Tagish Lake materials may also be spectral-compositional analogues for materials on the surfaces of other dark asteroids, including some that are targets of upcoming spacecraft missions. Tagish Lake has been proposed as a spectral match for 'ultra-primitive' D or P-type asteroids, and the variability reported here may be reflected in spatially or rotationally-resolved spectra of possible Tagish Lake parent bodies and source objects in the Near-Earth Asteroid population. A search for objects with spectra similar to Tagish Lake has been carried

  7. Intermolecular interaction as the origin of red shifts in absorption spectra of zinc-phthalocyanine from first-principles.

    PubMed

    Yanagisawa, Susumu; Yasuda, Taiga; Inagaki, Kouji; Morikawa, Yoshitada; Manseki, Kazuhiro; Yanagida, Shozo

    2013-11-01

    We investigate electronic origins of a redshift in absorption spectra of a dimerized zinc phthalocyanine molecule (ZnPc) by means of hybrid density functional theoretical calculations. In terms of the molecular orbital (MO) picture, the dimerization splits energy levels of frontier MOs such as the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the constituent molecules. Consequently, the absorption wavelength seems to become longer than the monomer as the overlap between the monomers becomes larger. However, for a ZnPc dimer configuration with its cofacially stacked monomer arrangement, the calculated absorption spectra within the time-dependent density functional theory indicates no redshift but blueshift in the Q-band absorption spectrum, i.e., a typical H-aggregate. The origin of the apparently contradictory result is elucidated by the conventional description of the interaction between monomer transition dipoles in molecular dimers [Kasha, M. Radiat. Res. 1963, 20, 55]. The redshift is caused by an interaction between the two head-to-tail transition dipoles of the monomers, while the side-by-side arranged transition dipoles result in a blueshift. By tuning the dipole-dipole interaction based on the electronic natures of the HOMO and the LUMO, we describe a slipped-stacked ZnPc dimer configuration in which the Q-band absorption wavelength increases by as large as 144 nm relative to the monomer Q-band. PMID:24106753

  8. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    NASA Astrophysics Data System (ADS)

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-07-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics.

  9. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    PubMed Central

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  10. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera.

    PubMed

    Wan, Yuhang; Carlson, John A; Kesler, Benjamin A; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A; Lim, Sung Jun; Smith, Andrew M; Dallesasse, John M; Cunningham, Brian T

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid's absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  11. Terbium chloride--aluminum chloride vapor system. I. Absorption and excitation spectra

    SciTech Connect

    Caird, J.A.; Carnall, W.T.; Hessler, J.P.; Williams, C.W.

    1981-01-15

    The absorption spectrum of the vapor complex formed at elevated temperatures between TbCl/sub 3/ and AlCl/sub 3/ has been measured in the region 20 000--50 000 cm/sup -1/. Oscillator strengths of f--f absorption bands below 37 000 cm/sup -1/ were determined. Strong absorption due to opposite parity 4f/sup 7/5d states was observed in the 37 000 to 50 000 cm/sup -1/ region with a peak molar absorptivity of approximately 500 l/mol cm. Significant additional absorption attributed to a molecular complex was also observed in this region. By measuring the excitation spectrum it was found that the molecular absorption does not appear to lead to fluorescence of the /sup 5/D/sub 4/ state. In contrast, absorption by the 4f/sup 7/5d states does result in strong /sup 5/D/sub 4/ fluorescence.

  12. How Van der Waals Interactions Influence the Absorption Spectra of Pheophorbide a Complexes: A Mixed Quantum-Classical Study.

    PubMed

    Megow, Jörg

    2015-10-01

    The computation of dispersive site energy shifts due to van der Waals interaction (London dispersion forces) was combined with mixed quantum-classical methodology to calculate the linear optical absorption spectra of large pheophorbide a (Pheo) dendrimers. The computed spectra agreed very well with the measurements considering three characteristic optical features occurring with increasing aggregate size: a strong line broadening, a redshift, and a low-energy shoulder. The improved mixed quantum-classical methodology is considered a powerful tool in investigating molecular aggregates. PMID:26275373

  13. X-ray Absorption Studies in Spinel-Type LiMn 2O 4

    NASA Astrophysics Data System (ADS)

    Liu, R. S.; Jang, L. Y.; Chen, J. M.; Tsai, Y. C.; Hwang, Y. D.; Liu, R. G.

    1997-02-01

    The electronic structure of the spinel-type LiMn2O4as the cathode material for the application in secondary batteries was probed using both MnK- andL23-edge X-ray absorption near edge structure (XANES) spectra. Based on the energy shifts of the absorption peaks in the XANES spectrum correlated to the effective charge, the valence of Mn in LiMn2O4was determined to be ∼4+. This suggests that the chemical substitution of low valent Li+ions into the Mn sites is possible to result in high valence of Mn.

  14. Local structure of indium oxynitride from x-ray absorption spectroscopy

    SciTech Connect

    T-Thienprasert, J.; Onkaw, D.; Rujirawat, S.; Limpijumnong, S.; Nukeaw, J.; Sungthong, A.; Porntheeraphat, S.; Singkarat, S.

    2008-08-04

    Synchrotron x-ray absorption near edge structures (XANES) measurements of In L{sub 3} edge is used in conjunction with first principles calculations to characterize rf magnetron sputtered indium oxynitride at different O contents. Good agreement between the measured and the independently calculated spectra are obtained. Calculations show that the XANES spectra of this alloy are sensitive to the coordination numbers of the In atoms, i.e., fourfold for indium nitride-like structures and sixfold for indium oxide-like structures, but not to the substitution of nearest neighbor N by O or vice versa.

  15. Electronic structure and optical absorption spectra of CdSe covered with ZnSe and ZnS epilayers

    NASA Astrophysics Data System (ADS)

    Yun, So Jeong; Lee, Geunsik; Kim, Jai Sam; Shin, Seung Koo; Yoon, Young-Gui

    2006-02-01

    Using the first-principles methods we compute the electronic structure and the absorption spectra for a wurtzite CdSe (0001) slab covered with zincblende ZnSe and ZnS epilayers. For each structure we compute the DOS and the imaginary part of the dielectric function. We find that the semiconductor passivation shifts the 'near Fermi-level' states of the bare CdSe slab down to lower energy levels. The migration suggests the decrease of surface effects and energy loss. We observe the substantial reduction of the abnormal peaks in the absorption spectra of the bare CdSe slab, which seems to be a consequence of the DOS migration. This is consistent with the experimental results that a proper passivation enhance the luminescence efficiency. We also study the case that the epilayer surface is terminated with PH 3 and find the PH 3 passivation also reduces the surface state to some extent.

  16. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Principal Hugoniot and K-shell X-ray absorption spectra of warm dense KCl are calculated using the first-principles molecular dynamics (FPMD) method. Evolution of electronic structures as well as the influence of the approximate description of ionization on pressure (caused by the underestimation of the energy gap between conduction bands and valence bands) in the first-principles method are illustrated by the calculation. It is shown that approximate description of ionization in FPMD has small influence on Hugoniot pressure due to mutual compensation of electronic kinetic pressure and virial pressure. The calculation of X-ray absorption spectra shows that the band gap of KCl persists after the pressure ionization of the 3p electrons of Cl and K taking place at lower energy, which provides a detailed understanding to the evolution of electronic structures of warm dense matter.

  17. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    SciTech Connect

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

    2015-06-15

    Principal Hugoniot and K-shell X-ray absorption spectra of warm dense KCl are calculated using the first-principles molecular dynamics (FPMD) method. Evolution of electronic structures as well as the influence of the approximate description of ionization on pressure (caused by the underestimation of the energy gap between conduction bands and valence bands) in the first-principles method are illustrated by the calculation. It is shown that approximate description of ionization in FPMD has small influence on Hugoniot pressure due to mutual compensation of electronic kinetic pressure and virial pressure. The calculation of X-ray absorption spectra shows that the band gap of KCl persists after the pressure ionization of the 3p electrons of Cl and K taking place at lower energy, which provides a detailed understanding to the evolution of electronic structures of warm dense matter.

  18. Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra

    SciTech Connect

    Meyer, Wilfried; Frommhold, Lothar

    2015-09-21

    Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He–Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D{sub 7} is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

  19. Research program in nuclear and solid state physics. [including pion absorption spectra and muon spin precession

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The survey of negative pion absorption reactions on light and medium nuclei was continued. Muon spin precession was studied using an iron target. An impulse approximation model of the pion absorption process implied that the ion will absorb almost exclusively on nucleon pairs, single nucleon absorption being suppressed by energy and momentum conservation requirements. For measurements on both paramagnetic and ferromagnetic iron, the external magnetic field was supplied by a large C-type electromagnet carrying a current of about 100 amperes.

  20. pH-Induced changes in electronic absorption and fluorescence spectra of phenazine derivatives

    NASA Astrophysics Data System (ADS)

    Ryazanova, O. A.; Voloshin, I. M.; Makitruk, V. L.; Zozulya, V. N.; Karachevtsev, V. A.

    2007-04-01

    The visible electronic absorption and fluorescence spectra as well as fluorescence polarization degrees of imidazo-[4,5-d]-phenazine (F1), 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), 1,2,3-triazole-[4,5-d]-phenazine (F4) and their glycosides, imidazo-[4,5-d]-phenazine-N1-β- D-ribofuranoside (F1rib), 1,2,3-triazole-[4,5-d]-phenazine-N1-β- D-glucopyranoside (F4gl), were investigated in aqueous buffered solutions over the pH range of 0-12, where the spectral transformations were found to be reversible. The effects of protonation and deprotonation on spectral properties of these dyes were studied. We have determined the ranges of pH, where individual ionic species are predominant. In aqueous buffered solutions the fluorescence was found only for neutral species of F1, F1rib, F2, and F4gl dyes, whereas for the ionic forms of these dyes, as well as for F3 and F4 ones, the fluorescence has not been detected. The concentrational deprotonation p Ka values were evaluated from experimental data. It was shown that donor-acceptor properties of the substituent group in the second position of the pentagonal ring substantially affect the values of the deprotonation constants and the character of protonation for chromophore. The substitution of a hydrogen atom in the NH-group by the sugar residue blocks the formation of the anionic species, and results in enhancement of the dye emission intensity. The steep emission dependence for F1 and F1rib over pH range of 0-7 with intensities ratio of IpH 7/ IpH 1 = 60 allows us to propose them as possible indicator dyes in luminescence based pH sensors for investigation of processes accompanied by acidification, e.g. as gastric pH-sensors. A comparative analysis of the studied dyes has shown that F4gl is the most promising compound to be used as a fluorescent probe for investigation of molecular hybridization of nucleic acids.

  1. 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.

  2. 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.

  3. Multiple Scattering Approach to Polarization Dependence of F K-Edge XANES Spectra for Highly Oriented Polytetrafluoroethylene (PTFE) Thin Film

    SciTech Connect

    Nagamatsu, S.; Ono, M.; Kera, S.; Okudaira, K. K.; Fujikawa, T.; Ueno, N.

    2007-02-02

    The polarization dependence of F K-edge X-ray absorption near edge structure (XANES) spectra of highly-oriented thin-film of polytetrafluoroethylene (PTFE) has been analyzed by using multiple scattering theory. The spectra show clear polarization dependence due to the highly-oriented structure. The multiple scattering calculations reflects a local structure around an absorbing atom. The calculated results obtained by considering intermolecular-interactions are in good agreement with the observed polarization-dependence. We have also analyzed structural models of the radiation damaged PTFE films.

  4. Effects of annealing treatment and gamma irradiation on the absorption and fluorescence spectra of Cr:GSGG laser crystal

    NASA Astrophysics Data System (ADS)

    Sun, D. L.; Luo, J. Q.; Xiao, J. Z.; Zhang, Q. L.; Jiang, H. H.; Yin, S. T.; Wang, Y. F.; Ge, X. W.

    2008-09-01

    The influence of annealing treatments and gamma-ray irradiation on the absorption and fluorescence spectra of Cr:GSGG crystals grown by the Czochralski method has been investigated. Two absorption bands located near 686 nm and 1050 nm were weakened markedly after the crystal was re-annealed in H2 atmosphere, which is due to the Cr4+ ions being de-oxidized into Cr3+ ions. The other two weak additional absorption bands induced by gamma-ray irradiation appearing near 310 nm and 480 nm are ascribed to the Fe2+ ions and F-type color centers, respectively. In particular, the gamma-ray irradiation with a dose of 100 Mrad has an effect of improving slightly the luminescence properties of Cr:GSGG crystals. The improvement mechanism is analyzed and discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    SciTech Connect

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

    2015-03-07

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

  7. Quantum mechanical calculation of the collision-induced absorption spectra of N2-N2 with anisotropic interactions.

    PubMed

    Karman, Tijs; Miliordos, Evangelos; Hunt, Katharine L C; Groenenboom, Gerrit C; van der Avoird, Ad

    2015-02-28

    We present quantum mechanical calculations of the collision-induced absorption spectra of nitrogen molecules, using ab initio dipole moment and potential energy surfaces. Collision-induced spectra are first calculated using the isotropic interaction approximation. Then, we improve upon these results by considering the full anisotropic interaction potential. We also develop the computationally less expensive coupled-states approximation for calculating collision-induced spectra and validate this approximation by comparing the results to numerically exact close-coupling calculations for low energies. Angular localization of the scattering wave functions due to anisotropic interactions affects the line strength at low energies by two orders of magnitude. The effect of anisotropy decreases at higher energy, which validates the isotropic interaction approximation as a high-temperature approximation for calculating collision-induced spectra. Agreement with experimental data is reasonable in the isotropic interaction approximation, and improves when the full anisotropic potential is considered. Calculated absorption coefficients are tabulated for application in atmospheric modeling. PMID:25725730

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

    PubMed

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

    2015-03-01

    A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters. PMID:25747062

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

    NASA Astrophysics Data System (ADS)

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

    2002-07-01

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

  10. The bispectrum of the Lyman α forest at z~ 2-2.4 from a large sample of UVES QSO absorption spectra (LUQAS)

    NASA Astrophysics Data System (ADS)

    Viel, M.; Matarrese, S.; Heavens, A.; Haehnelt, M. G.; Kim, T.-S.; Springel, V.; Hernquist, L.

    2004-01-01

    We present a determination of the bispectrum of the flux in the Lyman α forest of quasi-stellar object (QSO) absorption spectra obtained from a large sample of Ultraviolet Echelle Spectrograph (UVES) QSO absorption spectra (LUQAS), which consists of spectra observed with the high-resolution UVES. Typical errors on the observed bispectrum as obtained from a jack-knife estimator are ~ 50 per cent. For wavenumbers in the range 0.03 < k < 0.1 s km-1 the observed bispectrum agrees within the errors with that of the synthetic absorption spectra obtained from numerical hydro-simulations of a ΛCDM model with and without feedback from star formation. Including galactic feedback changes the bispectrum by less than 10 per cent. At smaller wavenumbers, the associated metal absorption lines contribute about 50 per cent to the bispectrum and the observed bispectrum exceeds that of the simulations. At wavenumbers k < 0.03 s km-1, second-order perturbation theory applied to the flux spectrum gives a reasonable (errors smaller than 30 per cent) approximation to the bispectra of observed and simulated absorption spectra. The bispectrum of the observed absorption spectra also agrees, within the errors, with that of a randomized set of absorption spectra where a random shift in wavelength has been added to absorption lines identified with VPFIT. This suggests that for a sample of the size presented here, the errors on the bispectrum are too large to discriminate between models with very different 3D distribution of Lyman α absorption. If it were possible to substantially reduce these errors for larger samples of absorption spectra, the bispectrum might become an important statistical tool for probing the growth of gravitational structure in the Universe at redshift z>~ 2.

  11. Electronic absorption spectra of imidazolium-based ionic liquids studied by far-ultraviolet spectroscopy and quantum chemical calculations.

    PubMed

    Tanabe, Ichiro; Kurawaki, Yuji; Morisawa, Yusuke; Ozaki, Yukihiro

    2016-08-10

    Electronic absorption spectra of imidazolium-based ionic liquids were studied by far- and deep-ultraviolet spectroscopy and quantum chemical calculations. The absorption spectra in the 145-300 nm region of imidazolium-based ionic liquids, [Cnmim](+)[BF4](-) (n = 2, 4, 8) and [C4mim](+)[PF6](-), were recorded using our original attenuated total reflectance (ATR) system spectrometer. The obtained spectra had two definitive peaks at ∼160 and ∼210 nm. Depending on the number of carbon atoms in the alkyl side chain, the peak wavelength around 160 nm changed, while that around 210 nm remained at almost the same wavelength. Quantum chemical calculation results based on the time-dependent density functional theory (TD-DFT) also showed the corresponding peak shifts. In contrast, there was almost no significant difference between [C4mim](+)[BF4](-) and [C4mim](+)[PF6](-), which corresponded with our calculations. Therefore, it can be concluded that the absorption spectra in the 145-300 nm region are mainly determined by the cations when fluorine-containing anions are adopted. In addition, upon addition of organic solvent (acetonitrile) to [C4mim](+)[BF4](-), small peak shifts to the longer wavelength were revealed for both peaks at ∼160 and ∼210 nm. The peak shift in the deep-ultraviolet region (≤200 nm) in the presence of the solvent, which indicates the change of electronic states of the ionic liquid, was experimentally observed for the first time by using the ATR spectrometer. PMID:27471106

  12. Correlation between Soft X-ray Absorption and Emission Spectra of the Nitrogen Atoms within Imidazolium-Based Ionic Liquids.

    PubMed

    Horikawa, Yuka; Tokushima, Takashi; Takahashi, Osamu; Hoke, Hiroshi; Takamuku, Toshiyuki

    2016-08-01

    Soft X-ray absorption spectroscopy (XAS) has been performed on the N K-edge of two imidazolium-based ionic liquids (ILs), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C2mim][TFSA]) and 1-ethyl-3-methylimidazolium bromide ([C2mim][Br]), to clarify the electronic structures of the ILs. Soft X-ray emission spectroscopy (XES) has also been applied to the ILs by excitation at various X-ray energies according to the XAS spectra. It was possible to fully associate the XAS peaks with the XES peaks. Additionally, both XAS and XES spectra of the ILs were well reproduced by the theoretical spectra for a single-molecule model on [C2mim](+) and [TFSA](-) using density functional theory. The assignments for the XAS and XES peaks of the ILs were accomplished from both experimental and theoretical approaches. The theoretical XAS and XES spectra of [C2mim](+) and [TFSA](-) did not significantly depend on the conformations of the ions. The reproducibility of the theoretical spectra for the single-molecule model suggested that the interactions between the cations and anions are very weak in the ILs, thus scarcely influencing the electronic structures of the nitrogen atoms. PMID:27388151

  13. Sticking to (first) principles: quantum molecular dynamics and Bayesian probabilistic methods to simulate aquatic pollutant absorption spectra.

    PubMed

    Trerayapiwat, Kasidet; Ricke, Nathan; Cohen, Peter; Poblete, Alex; Rudel, Holly; Eustis, Soren N

    2016-08-10

    This work explores the relationship between theoretically predicted excitation energies and experimental molar absorption spectra as they pertain to environmental aquatic photochemistry. An overview of pertinent Quantum Chemical descriptions of sunlight-driven electronic transitions in organic pollutants is presented. Second, a combined molecular dynamics (MD), time-dependent density functional theory (TD-DFT) analysis of the ultraviolet to visible (UV-Vis) absorption spectra of six model organic compounds is presented alongside accurate experimental data. The functional relationship between the experimentally observed molar absorption spectrum and the discrete quantum transitions is examined. A rigorous comparison of the accuracy of the theoretical transition energies (ΔES0→Sn) and oscillator strength (fS0→Sn) is afforded by the probabilistic convolution and deconvolution procedure described. This method of deconvolution of experimental spectra using a Gaussian Mixture Model combined with Bayesian Information Criteria (BIC) to determine the mean (μ) and standard deviation (σ) as well as the number of observed singlet to singlet transition energy state distributions. This procedure allows a direct comparison of the one-electron (quantum) transitions that are the result of quantum chemical calculations and the ensemble of non-adiabatic quantum states that produce the macroscopic effect of a molar absorption spectrum. Poor agreement between the vertical excitation energies produced from TD-DFT calculations with five different functionals (CAM-B3LYP, PBE0, M06-2X, BP86, and LC-BLYP) suggest a failure of the theory to capture the low energy, environmentally important, electronic transitions in our model organic pollutants. However, the method of explicit-solvation of the organic solute using the quantum Effective Fragment Potential (EFP) in a density functional molecular dynamics trajectory simulation shows promise as a robust model of the hydrated organic

  14. SYNCHROTRON POLARIZATION AND SYNCHROTRON SELF-ABSORPTION SPECTRA FOR A POWER-LAW PARTICLE DISTRIBUTION WITH FINITE ENERGY RANGE

    SciTech Connect

    Fouka, M.; Ouichaoui, S. E-mail: souichaoui@usthb.dz

    2011-12-10

    We have derived asymptotic forms for the degree of polarization of the optically thin synchrotron and for synchrotron self-absorption (SSA) spectra assuming a power-law particle distribution of the form N({gamma}) {approx} {gamma}{sup -p} with {gamma}{sub 1} < {gamma} < {gamma}{sub 2}, especially for a finite high-energy limit, {gamma}{sub 2}, in the case of an arbitrary pitch angle. The new results inferred concern more especially the high-frequency range x >> {eta}{sup 2} with parameter {eta} = {gamma}{sub 2}/{gamma}{sub 1}. The calculated SSA spectra concern instantaneous photon emission where cooling effects are not considered. They have been obtained by also ignoring likely effects such as Comptonization, pair creation and annihilation, as well as magnetic photon splitting. To that aim, in addition to the two usual absorption frequencies, a third possible one has been derived and expressed in terms of the Lambert W function based on the analytical asymptotic form of the absorption coefficient, {alpha}{sub {nu}}, for the high-frequency range {nu} >> {nu}{sub 2} (with {nu}{sub 2} the synchrotron frequency corresponding to {gamma}{sub 2}). We have shown that the latter frequency may not have realistic applications in astrophysics, except in the case of an adequate set of parameters allowing one to neglect Comptonization effects. More detailed calculations and discussions are presented.

  15. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Liu, Zhongfang; Liu, Jiangtao; Liu, Shaopu; Shen, Wei

    2008-03-01

    In pH 4.4-4.5 Britton-Robinson (BR) buffer solution, fluoroquinolone antibiotics (FLQs) including ciprofloxacin (CIP), norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) could react with erythrosine (Ery) to form 1:1 ion-association complexes, which not only resulted in the changes of the absorption spectra and the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS). These offered some indications of the determination of fluoroquinolone antibiotics by spectrophotometric, fluorescence and resonance Rayleigh scattering methods. The detection limits for fluoroquinolone antibiotics were in the range of 0.097-0.265 μg/mL for absorption methods, 0.022-0.100 μg/mL for fluorophotometry and 0.014-0.027 μg/mL for RRS method, respectively. Among them, the RRS method had the highest sensitivity. In this work, the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions and the properties of the analytical chemistry were investigated. The methods have been successfully applied to determination of some fluoroquinolone antibiotics in human urine samples and tablets. Taking CIP-Ery system as an example, the charge distribution, the enthalpy of formation and the mean polarizability were calculated by density function theory (DFT) method. In addition, the reasons for the enhancement of scattering spectra were discussed.

  16. High resolution infrared absorption spectra of various trace gases present in the upper atmosphere of the Earth

    NASA Technical Reports Server (NTRS)

    Hunt, Robert H.

    1988-01-01

    The objective of NASA Grant NsG 7473 was to obtain and analyze high resolution infrared absorption spectra of various trace gases present in the Earth's upper atmosphere. The goal of the spectral analysis was to obtain values of absorption line strengths, widths and frequencies of sufficient accuracy for use in upper atmosphere trace gas monitoring. During the early phase of the grant, high resolution spectra were obtained from two instruments. One was the 0.02/cm resolution vacuum grating spectrometer at the Florida State University and the other was the 0.01/cm resolution Fourier transform spectrometer at the McMath solar telescope at the Kitt Peak Observatory. Using these instruments, a considerable amount of spectra of methane and hydrogen peroxide were obtained and analyzed. During the latter years of the project, data taking was halted while efforts were devoted to building a new 0.0025/cm resolution vacuum Fourier transform spectrometer. Progress during this phase of the grant then became greatly slowed due to a lack of suitable graduate students in the program. However, the instrument was completed and brought to the point of producing interferograms.

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

    SciTech Connect

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

    2014-06-20

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

  18. Extraction of pigment information from near-UV vis absorption spectra of extra virgin olive oils.

    PubMed

    Domenici, Valentina; Ancora, Donatella; Cifelli, Mario; Serani, Andrea; Veracini, Carlo Alberto; Zandomeneghi, Maurizio

    2014-09-24

    This work reports a new approach to extract the maximum chemical information from the absorption spectrum of extra virgin olive oils (EVOOs) in the 390-720 nm spectral range, where "oil pigments" dominate the light absorption. Four most important pigments, i.e., two carotenoids (lutein and β-carotene) and two chlorophylls (pheophytin-a and pheophytin-b), are chosen as reference oil pigments, being present in all the reported analytical data regarding pigments of EVOOs. The method allows the quantification of the concentration values of these four pigments directly from the deconvolution of the measured absorption spectrum of EVOOs. Advantages and limits of the method and the reliability of the pigment family quantification are discussed. The main point of this work is the description of a fast and simple method to extract of such information in less than a minute, through the mathematical analysis of the UV-vis spectrum of untreated samples of oil. PMID:25178056

  19. Disentangling vibronic and solvent broadening effects in the absorption spectra of coumarin derivatives for dye sensitized solar cells.

    PubMed

    Cerezo, Javier; Avila Ferrer, Francisco J; Santoro, Fabrizio

    2015-05-01

    We simulate from first-principles the absorption spectra of five structure-related coumarin derivatives utilized in dye sensitized solar cells (DSSCs), investigating the vibronic and solvent contributions to the position and width of the spectra in ethanol. Ground and excited state potential energy surfaces (PESs) are modeled by Density Functional Theory (DFT) and its time-dependent (TD) expression for the excited state (TD-DFT). The solute vibronic structure associated with the spectrum is calculated by a TD formalism, accounting for both Duschinsky and temperature effects, while solvent inhomogeneous broadening is evaluated according to Marcus' theory, computing the solvent reorganization energy by the state-specific implementation of the polarizable continuum model (PCM) within TD-DFT. We adopted both the standard hybrid PBE0 and the range separated CAM-B3LYP functionals showing that the latter performs better both concerning the vibronic and solvent-induced contributions to the absorption lineshape. The different predictions of the two functionals are then rationalized in terms of the charge transfer (CT) character of the transitions showing that, in this class of compounds, it is strongly dependent on the nuclear structure. Such a dependence introduces a bias in the PBE0 PES that has a drastic impact on the vibronic spectra. We show that both the intrinsic vibronic structure and the solvent broadening play a relevant role in differentiating the absorption width of the five dyes. In this sense, our results provide a guide to understand the sources of spectral broadening of this family of dyes, a valuable help for a rational design of new molecules to improve DSSC devices. PMID:25848730

  20. A panchromatic modification of the light absorption spectra of metal-organic frameworks.

    PubMed

    Otal, E H; Kim, M L; Calvo, M E; Karvonen, L; Fabregas, I O; Sierra, C A; Hinestroza, J P

    2016-05-10

    The optical absorption of UiO-66-NH2 MOF was red-shifted using a diazo-coupling reaction. The modifications performed with naphthols and aniline yielded reddish samples, and the modifications with diphenylaniline yielded dark violet ones. The photocatalytic activity of these modified MOFs was assessed for methylene blue degradation, showing a good performance relative to traditional TiO2. The degradation performance was found to correlate with the red shift of the absorption edge. These findings suggest potential applications of these materials in photocatalysis and in dye sensitized solar cells. PMID:27071816

  1. 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

  2. Asymmetric and symmetric absorption peaks observed in infrared spectra of CO2 adsorbed on TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Sato, Yoshinori; Fukutani, Katsuyuki

    2016-04-01

    Infrared spectra of CO2 physisorbed on titania nanotubes (TiNTs), predominantly in the anatase polymorph, were measured at 81 K. Asymmetric and symmetric absorption peaks due to the antisymmetric stretch vibration (ν3) of CO2 were observed at 2340 cm-1 and 2350 cm-1, respectively. On the basis of the exposure- and time-dependence of the spectrum, the 2340 cm-1 peak was attributed to CO2 at the defective sites related to subsurface O vacancies (Vos) while the 2350 cm-1 peak was assigned to that at the fivefold coordinated Ti4+ sites. It was found that the generalized Fano line shape was well fitted to the 2340 cm-1 peak. We also observed an absorption peak at 2372 cm-1, which was attributed to the combination band of ν3 and the external mode of CO2 at Ti4+.

  3. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  5. Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction

    PubMed Central

    2015-01-01

    We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Δm is mainly caused by dispersion effects and depends sensitively on the molecule’s specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Δm= −QWm in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while Wm is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI). PMID:25834658

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  7. Absorption spectra of two-level atoms interacting with a strong polychromatic pump field and an arbitrarily intense probe field

    NASA Astrophysics Data System (ADS)

    Yoon, Tai Hyun; Chung, Myung Sai; Lee, Hai-Woong

    1999-09-01

    A numerical method is introduced that solves the optical Bloch equations describing a two-level atom interacting with a strong polychromatic pump field with an equidistant spectrum and an arbitrarily intense monochromatic probe field. The method involves a transformation of the optical Bloch equations into a system of equations with time-independent coefficients at steady state via double harmonic expansion of the density-matrix elements, which is then solved by the method of matrix inversion. The solutions so obtained lead immediately to the determination of the polarization of the atomic medium and of the absorption and dispersion spectra. The method is applied to the case when the pump field is bichromatic and trichromatic, and the physical interpretation of the numerically computed spectra is given.

  8. Spectra Aerosol Light Scattering and Absorption for Laboratory and Urban Aerosol

    NASA Astrophysics Data System (ADS)

    Gyawali, Madhu S.

    Atmospheric aerosols considerably influence the climate, reduce visibility, and cause problems in human health. Aerosol light absorption and scattering are the important factors in the radiation transfer models. However, these properties are associated with large uncertainties in climate modeling. In addition, atmospheric aerosols widely vary in composition and size; their optical properties are highly wavelength dependent. This work presents the spectral dependence of aerosol light absorption and scattering throughout the ultraviolet to near-infrared regions. Data were collected in Reno, NV from 2008 to 2010. Also presented in this study are the aerosol optical and physical properties during carbonaceous aerosols and radiative effects study (CARES) conducted in Sacramento area during 2010. Measurements were made using photoacoustic instruments (PA), including a novel UV 355 nm PA of our design and manufacture. Comparative analyses are presented for three main categories: (1) aerosols produced by wildfires and traffic emissions, (2) laboratory-generated and wintertime ambient urban aerosols, and (3) urban plume and biogenic emissions. In these categories, key questions regarding the light absorption by secondary organic aerosols (SOA), so-called brown carbon (BrC), and black carbon (BC) will be discussed. An effort is made to model the emission and aging of urban and biomass burning aerosol by applying shell-core calculations. Multispectral PA measurements of aerosols light absorption and scattering coefficients were used to calculate the Angstrom exponent of absorption (AEA) and single scattering albedo (SSA). The AEA and SSA values were analyzed to differentiate the aerosol sources. The California wildfire aerosols exhibited strong wavelength dependence of aerosol light absorption with AEA as lambda -1 for 405 and 870 nm, in contrast to the relatively weak wavelength dependence of traffic emissions aerosols for which AEA varied approximately as lambda-1. By using

  9. 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}.

  10. Effects of crossed electric and magnetic fields on the interband optical absorption spectra of variably spaced semiconductor superlattices

    NASA Astrophysics Data System (ADS)

    Zuleta, J. N.; Reyes-Gómez, E.

    2016-05-01

    The interband optical absorption spectra of a GaAs-Ga1-xAlxAs variably spaced semiconductor superlattice under crossed in-plane magnetic and growth-direction applied electric fields are theoretically investigated. The electronic structure, transition strengths and interband absorption coefficients are analyzed within the weak and strong magnetic-field regimes. A dramatic quenching of the absorption coefficient is observed, in the weak magnetic-field regime, as the applied electric field is increased, in good agreement with previous experimental measurements performed in a similar system under growth-direction applied electric fields. A decrease of the resonant tunneling in the superlattice is also theoretically obtained in the strong magnetic-field regime. Moreover, in this case, we found an interband absorption coefficient weakly dependent on the applied electric field. Present theoretical results suggest that an in-plane magnetic field may be used to tune the optical properties of variably spaced semiconductor superlattices, with possible future applications in solar cells and magneto-optical devices.

  11. Absolute absorption spectra of batho- and photorhodopsins at room temperature. Picosecond laser photolysis of rhodopsin in polyacrylamide.

    PubMed Central

    Kandori, H; Shichida, Y; Yoshizawa, T

    1989-01-01

    Picosecond laser photolysis of rhodopsin in 15% polyacrylamide gel was performed for estimating absolute absorption spectra of the primary intermediates of cattle rhodopsin (bathorhodopsin and photorhodopsin). Using a rhodopsin digitonin extract embedded in 15% polyacrylamide gel, a precise percentage of bleaching of rhodopsin after excitation of a picosecond laser pulse was measured. Using this value, the absolute absorption spectrum of bathorhodopsin was calculated from the spectral change before and 1 ns after the picosecond laser excitation (corresponding to the difference spectrum between rhodopsin and bathorhodopsin). The absorption spectrum of bathorhodopsin thus obtained displayed a lambda max at 535 nm, which was shorter than that at low temperature (543 nm) and a half band-width broader than that measured at low temperature. The oscillator strength of bathorhodopsin at room temperature was smaller than that at low temperature. The absolute absorption spectrum of photorhodopsin was also estimated from the difference spectrum measured at 15 ps after the excitation of rhodopsin (Shichida, Y., S. Matuoka, and T. Yoshizawa. 1984. Photobiochem. Photobiophys. 7:221-228), assuming a sequential conversion of photorhodopsin to bathorhodopsin. Its lambda max was located at approximately 570 nm, and the oscillator strength was smaller than those of rhodopsin and bathorhodopsin. PMID:2790133

  12. Electronic properties and absorption spectra of ZnSnP{sub 2} using mBJ potential

    SciTech Connect

    Joshi, Ritu Ahuja, B. L.

    2015-06-24

    We present the energy bands and density of states of ZnSnP{sub 2} using full potential linearized augmented plane wave method with modified Becke Johnson potential. It is found that this compound has a direct band gap of about 2.01 eV at Γ point, which originates from the energy difference between P-3p and Sn-5s states. In addition, we have also calculated absorption spectra in the solar energy range and compared it with that of bulk Si to explore the applicability of ZnSnP{sub 2} in photovoltaic and optoelectronic devices.

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

    PubMed

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

    2016-02-15

    The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6 ](3-) and [Fe(CN)6 ](3-) . For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double-ζ basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems. PMID:26502979

  14. 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.

  15. 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.

  16. Using of laser spectroscopy and chemometrics methods for identification of patients with lung cancer, patients with COPD and healthy people from absorption spectra of exhaled air

    NASA Astrophysics Data System (ADS)

    Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Nikiforova, Olga Yu.; Ponomarev, Yurii N.; Tuzikov, Sergei A.; Yumov, Evgeny L.

    2014-11-01

    The results of application of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with chronic respiratory diseases (chronic obstructive pulmonary disease and lung cancer) are presented. The absorption spectra of exhaled breath of representatives of the target groups and healthy volunteers were measured; the selection by chemometrics methods of the most informative absorption coefficients in scan spectra in terms of the separation investigated nosology was implemented.

  17. A Simple Experiment Demonstrating the Relationship between Response Curves and Absorption Spectra.

    ERIC Educational Resources Information Center

    Li, Chia-yu

    1984-01-01

    Describes an experiment for recording two individual spectrophotometer response curves. The two curves are directly related to the power of transmitted beams that pass through a solvent and solution. An absorption spectrum of the solution can be constructed from the calculated rations of the curves as a function of wavelength. (JN)

  18. Determination of vibration-rotation lines intensities from absorption Fourier spectra

    NASA Technical Reports Server (NTRS)

    Mandin, J. Y.

    1979-01-01

    The method presented allows the line intensities to be calculated from either their equivalent widths, heights, or quantities deduced from spectra obtained by Fourier spectrometry. This method has proven its effectiveness in measuring intensities of 60 lines of the molecule H2O with a precision of 10%. However, this method cannot be applied to isolated lines.

  19. High-Resolution Ultraviolet Spectra of the Dwarf Seyfert 1 Galaxy NGC 4395: Evidence for Intrinsic Absorption

    NASA Astrophysics Data System (ADS)

    Crenshaw, D. M.; Kraemer, S. B.; Gabel, J. R.; Schmitt, H. R.; Filippenko, A. V.; Ho, L. C.; Shields, J. C.; Turner, T. J.

    2004-09-01

    We present ultraviolet spectra of the dwarf Seyfert 1 nucleus of NGC 4395, obtained with the Far Ultraviolet Spectroscopic Explorer (FUSE) and the Hubble Space Telescope Space Telescope Imaging Spectrograph at velocity resolutions of 7-15 km s-1. We confirm our earlier claim of C IV absorption in low-resolution UV spectra and detect a number of other absorption lines with lower ionization potentials. In addition to the Galactic lines, we identify two kinematic components of absorption that are likely to be intrinsic to NGC 4395. We consider possible origins of the absorption, including the interstellar medium (ISM) of NGC 4395, the narrow-line region, the outflowing UV absorbers, and the X-ray ``warm absorbers.'' Component 1, at a radial velocity of -770 km s-1 with respect to the nucleus, is only identified in the C IV λ1548.2 line. It most likely represents an outflowing UV absorber, similar to those seen in a majority of Seyfert 1 galaxies, although additional observations are needed to confirm the reality of this feature. Component 2, at -114 km s-1, most likely arises in the ISM of NGC 4395; its ionic column densities cannot be matched by photoionization models with a power-law continuum. Our models of the highly ionized X-ray absorbers claimed for this active galactic nucleus indicate that they would have undetectable C IV absorption, but large O VI and H I columns should be present. We attribute our lack of detection of the O VI and Lyβ absorption from the X-ray absorbers to a combination of noise and dilution of the nuclear spectrum by hot stars in the large FUSE aperture. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555 these observations are associated with proposal GO-9362. Also based on observations made with the NASA-CNES-CSA Far Ultraviolet Spectroscopic Explorer

  20. Electronic Absorption Spectra from MM and ab initio QM/MM Molecular Dynamics: Environmental Effects on the Absorption Spectrum of Photoactive Yellow Protein

    PubMed Central

    Isborn, Christine M.; Götz, Andreas W.; Clark, Matthew A.; Walker, Ross C.; Martínez, Todd J.

    2012-01-01

    We describe a new interface of the GPU parallelized TeraChem electronic structure package and the Amber molecular dynamics package for quantum mechanical (QM) and mixed QM and molecular mechanical (MM) molecular dynamics simulations. This QM/MM interface is used for computation of the absorption spectra of the photoactive yellow protein (PYP) chromophore in vacuum, aqueous solution, and protein environments. The computed excitation energies of PYP require a very large QM region (hundreds of atoms) covalently bonded to the chromophore in order to achieve agreement with calculations that treat the entire protein quantum mechanically. We also show that 40 or more surrounding water molecules must be included in the QM region in order to obtain converged excitation energies of the solvated PYP chromophore. These results indicate that large QM regions (with hundreds of atoms) are a necessity in QM/MM calculations. PMID:23476156

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

    ERIC Educational Resources Information Center

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

    2007-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Kurtz, Joe; Huffman, Donald R.

    1989-01-01

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

  3. Electronic absorption spectra of H₂C₆O⁺ isomers: produced by ion-molecule reactions.

    PubMed

    Chakraborty, Arghya; Fulara, Jan; Maier, John P

    2015-01-01

    Three absorption systems with origins at 354, 497, and 528 nm were detected after mass-selected deposition of H2C6O(+) in a 6 K neon matrix. The ions were formed by the reaction of C2O with HC4H(+) in a mixture of C3O2 and diacetylene in a hot cathode source, or by dissociative ionization of tetrabromocyclohexadienone. The 497 and 354 nm systems are assigned to the 1(2)A″ ← X(2)A″ and 2(2)A″ ← X(2)A″ electronic transitions of B(+), (2-ethynylcycloallyl)methanone cation, and the 528 nm absorption to the 1(2)A2 ← X(2)B1 transition of F(+), 2-ethynylbut-3-yn-1-enone-1-ylide, on the basis of calculated excitation energies with CASPT2. PMID:25495044

  4. Common lines in the rest-frame absorption-line spectra of QSOs?

    NASA Astrophysics Data System (ADS)

    Varshni, Y. P.; Singh, D.

    1985-02-01

    Libby et al. (1984) have studied the absorption-line data for 13 QSOs in the rest-frames of the QSOs. It is shown that the number of groups in which 5 lines or more lie within a wavelength interval of 1.0 Å found by these authors is insignificantly different from that that would be expected from chance coincidences. Consequently, there is no evidence that the rest-frame wavelengths at which these groups occur have any special significance.

  5. Phase-dependent absorption features in X-ray spectra of XDINSs

    NASA Astrophysics Data System (ADS)

    Borghese, A.; Rea, N.

    2016-06-01

    A detailed pulse phase spectroscopy using all the available XMM-Newton observations of X-ray dim isolated neutron stars (XDINSs) have revealed the presence of narrow and strongly phase-dependent absorption X-ray features. The first discovered was in the X-ray spectrum of the nearby XDINS RX J0720.4-3125. The line seems to be stable in time over a timespan of 12 years and is present in 20% of the pulsar rotation. Because of its narrow width and its strong dependency on the rotational phase, the spectral line is probably due to proton cyclotron absorption in a ˜10^{14} G confined magnetic structure (with a field strength about 7 times the dipolar field of this pulsar). Performing the same analysis to all archival XDINS data, a new possible candidate was found in the X-ray spectrum of RX J1308.6+2127. This absorption feature shows the same phase dependency and energy as the first one, revealing the presence of a high-B structure close to the stellar surface. This result supports the proposed scenario of XDINSs being aged magnetars, having still a strong non-dipolar crustal B-field component.

  6. Interaction of chlorophyll with light: Calculations of absorption spectra and dichroism with a new technique

    NASA Astrophysics Data System (ADS)

    Hamilton, Robert Bryan

    1999-12-01

    The response of a single chlorophyll molecule to light was studied using a semiempirical tight-binding model together with the Peierls substitution. Over a range of wavelengths, the absorption was calculated for unpolarized, linearly polarized, and circularly polarized light. The results are consistent with previous experiments, although detailed comparisons are not possible because the experiments involve chlorophyll molecules in more complicated environments. For unpolarized light, the absorption peaks in the red part of the visible spectrum. There is a secondary shoulder in the blue. For linearly polarized light, the absorption depends on wavelength and the direction of polarization. This can be understood as arising from the joint density of states for transitions at each photon energy, together with matrix-element effects (both of which are included in the present formulation). For circular polarization, the dichroism as a function of wavelength is slightly more subtle, but again can be understood in terms of matrix elements for the states involved in a transition at a given photon energy. We also found that an ``effective helicity'' is useful in understanding the circular dichroism. One advantage of the method used here is that it can be employed for other molecules that are important in photobiology-for example, retinal and melanin.

  7. 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

  8. Simulation of Vacuum UV Absorption and Electronic Circular Dichroism Spectra of Methyl Oxirane: The Role of Vibrational Effects.

    PubMed

    Hodecker, Manuel; Biczysko, Malgorzata; Dreuw, Andreas; Barone, Vincenzo

    2016-06-14

    Vibrationally resolved one-photon absorption and electronic circular dichroism spectra of (R)-methyl oxirane were calculated with different electronic and vibronic models selecting, through an analysis of the convergence of the results, the best compromise between reliability and computational cost. Linear-response TD-DFT/CAM-B3LYP/SNST electronic computations in conjunction with the simple vertical gradient vibronic model were chosen and employed for systematic comparison with the available experimental data. Remarkable agreement between simulated and experimental spectra was achieved for both one-photon absorption and circular dichroism concerning peak positions, relative intensities, and general spectral shapes considering the computational efficiency of the chosen theoretical approach. The significant improvement of the results with respect to smearing of vertical electronic transitions by phenomenological Gaussian functions and the possible inclusion of solvent effects by polarizable continuum models at a negligible additional cost paves the route toward the simulation and analysis of spectral shapes of complex molecular systems in their natural environment. PMID:27159495

  9. Study of absorption spectra of gasolines and other hydrocarbon mixtures in the second overtone region of the CH3, CH2, CH groups

    NASA Astrophysics Data System (ADS)

    Muradov, V. G.; Sannikov, D. G.

    2007-03-01

    We have obtained experimental and model absorption spectra for individual hydrocarbons (toluene, benzene, n-heptane, and iso-octane) and their mixtures in the near IR range (λ = 1080 1220 nm). We model the spectra of nonsynthetic gasolines obtained under the same conditions by combining the spectra of three pure hydrocarbons. We show that the octane number of the studied gasoline is linearly related to the toluene (or benzene) concentrations in the model mixture.

  10. Spectral investigations of 2,5-difluoroaniline by using mass, electronic absorption, NMR, and vibrational spectra

    NASA Astrophysics Data System (ADS)

    Kose, Etem; Karabacak, Mehmet; Bardak, Fehmi; Atac, Ahmet

    2016-11-01

    One of the most significant aromatic amines is aniline, a primary aromatic amine replacing one hydrogen atom of a benzene molecule with an amino group (NH2). This study reports experimental and theoretical investigation of 2,5-difluoroaniline molecule (2,5-DFA) by using mass, ultraviolet-visible (UV-vis), 1H and 13C nuclear magnetic resonance (NMR), Fourier transform infrared and Raman (FT-IR and FT-Raman) spectra, and supported with theoretical calculations. Mass spectrum (MS) of 2,5-DFA is presented with their stabilities. The UV-vis spectra of the molecule are recorded in the range of 190-400 nm in water and ethanol solvents. The 1H and 13C NMR chemical shifts are recorded in CDCl3 solution. The vibrational spectra are recorded in the region 4000-400 cm-1 (FT-IR) and 4000-10 cm-1 (FT-Raman), respectively. Theoretical studies are underpinned the experimental results as described below; 2,5-DFA molecule is optimized by using B3LYP/6-311++G(d,p) basis set. The mass spectrum is evaluated and possible fragmentations are proposed based on the stable structure. The electronic properties, such as excitation energies, oscillator strengths, wavelengths, frontier molecular orbitals (FMO), HOMO and LUMO energies, are determined by time-dependent density functional theory (TD-DFT). The electrostatic potential surface (ESPs), density of state (DOS) diagrams are also prepared and evaluated. In addition to these, reduced density gradient (RDG) analysis is performed, and thermodynamic features are carried out theoretically. The NMR spectra (1H and 13C) are calculated by using the gauge-invariant atomic orbital (GIAO) method. The vibrational spectra of 2,5-DFA molecule are obtained by using DFT/B3LYP method with 6-311++G(d,p) basis set. Fundamental vibrations are assigned based on the potential energy distribution (PED) of the vibrational modes. The nonlinear optical properties (NLO) are also investigated. The theoretical and experimental results give a detailed description of

  11. 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.

  12. Resonance Raman and vibronic absorption spectra with Duschinsky rotation from a time-dependent perspective: Application to β-carotene

    NASA Astrophysics Data System (ADS)

    Banerjee, Shiladitya; Kröner, Dominik; Saalfrank, Peter

    2012-12-01

    The time-dependent approach to electronic spectroscopy, as popularized by Heller and co-workers in the 1980s, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption and resonance Raman spectra of β-carotene, with and without a solvent. Two-state models, the harmonic and the Condon approximations are used in order to do so. A new code has been developed which includes excited state displacements, vibrational frequency shifts, and Duschinsky rotation, i.e., mode mixing, for both non-adiabatic spectroscopies. It is shown that Duschinsky rotation has a pronounced effect on the resonance Raman spectra of β-carotene. In particular, it can explain a recently found anomalous behaviour of the so-called ν1 peak in resonance Raman spectra [N. Tschirner, M. Schenderlein, K. Brose, E. Schlodder, M. A. Mroginski, C. Thomsen, and P. Hildebrandt, Phys. Chem. Chem. Phys. 11, 11471 (2009)], 10.1039/b917341b, which shifts with the change in excitation wavelength.

  13. Far-infrared absorption spectra and properties of SnO2 nanorods

    NASA Astrophysics Data System (ADS)

    Liu, Yingkai; Dong, Yi; Wang, Guanghou

    2003-01-01

    Gray-colored materials synthesized by calcining the precursor powders, which were produced in a microemulsion, are identified to be rutile structured SnO2 nanorods 20-45 nm in diameter and several micrometers in length by x-ray diffraction, transmission with electron microscopy, and high-resolution transmission microscopy. Conspicuous far-infrared (FIR) absorption spectrum platform peaks with widths of up to 61.6 and 119 cm-1 are observed, and are explained as the overlap of the surface modes of cylindrical and spheroid particles. Good agreement is achieved between FIR platform peaks and calculated results.

  14. Reflectance Spectra of Ureilites: Nature of the Mafic Silicate Absorption Features

    NASA Technical Reports Server (NTRS)

    Cloutis, E. A.; Hudon, P.

    2004-01-01

    Ureilites are unique carbon-bearing achondrites. They are composed primarily of olivine and pyroxene with minor amounts of finely dispersed matrix material consisting mostly of carbon, metal, sulfides and fine-grained silicates. As is the case with many classes of meteorites, no clear chain of evidence exists which can relate them to specific asteroidal parent bodies. In order to provide insights into parent body connections, visible and near-IR (VNIR) reflectance spectra of a number of ureilites have been measured and analyzed in light of their mineralogy.

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

    SciTech Connect

    Sargent, B. A.; Forrest, W.; Watson, Dan M.; Kim, K. H.; Richter, I.; Tayrien, C.; D'Alessio, P.; Calvet, N.; Furlan, E.; Green, J.; Pontoppidan, K.

    2014-09-10

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

  16. Absorption spectra and photovoltaic characterization of chlorophyllins as sensitizers for dye-sensitized solar cells.

    PubMed

    Calogero, Giuseppe; Citro, Ilaria; Crupi, Cristina; Di Marco, Gaetano

    2014-11-11

    Dye-sensitized solar cells (DSSCs) based on Chlorine-e6 (Chl-e6), a Chlorophyll a derivative, and Chl-e6 containing Cu, have been investigated by carrying out incident photon to current efficiency (IPCE) and current-voltage (I-V) measurements. The effect of the metallic ion and the influence of the solvent polarity on the dye aggregation and their absorption bands have been analysed by performing electronic absorption measurements. The dependence of the photoelectrochemical parameters of these DSSCs on the electrolyte by the addition of pyrimidine and/or pyrrole has been discussed in details. For the first time I-V curves for a DSSC based on copper Chl-e6 dye have been shown and compared with Zn based chlorophyllin. Furthermore, the performance of a Cu-Chl-e6 based DSSC has been deeply improved by a progressive optimization of the TiO2 multilayer photoanode overcoming the best data reported in literature so far for this dye. It's worth to emphasize that, the analysis reported in this paper supplies very useful information which paves the way to further detailed studies turned to the employment of natural pigments as sensitizers for solar cells. PMID:24892526

  17. Ly(alpha) emission and absorption features in the spectra of galaxies

    NASA Technical Reports Server (NTRS)

    Chen, W. L.; Neufeld, David A.

    1994-01-01

    The combined effects of interstellar dust absorption and of scattering by hydrogen atoms may give rise to a Ly(alpha) spectral feature of negative equivalent width, as has been observed in several star-forming galaxies. By considering the transfer of Ly(alpha) line radiation and of neighboring stellar continuum radiation within a dusty galaxy, we find that dust absorption has three effects: (1) it reduces the apparent ultraviolet continuum luminosity at all wavelengths; (2) it preferentially decreases the apparent Ly(alpha) line luminosity from H II regions; and (3) it creates an 'attenuation feature' in the continuum spectrum -- centered at the Ly(alpha) rest frequency -- which occurs because the attenuation of the stellar continuum radiation increases as the Ly(alpha) rest frequency is approached, due to the effects of scattering by hydrogen atoms. For plausible values of the galactic dust content and of the disk thickness, these effects can lead to a negative net Ly(alpha) equivalent width, even for galaxies in which the unattenuated spectrum would show a strong Ly(alpha) emission line.

  18. The Infrared Spectra and Absorption Intensities of Amorphous Ices: Methane and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and the interstellar medium, with an emphasis on amorphous and crystalline ices below ~70 K. Our goal is to add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on two of the simplest and most abundant components of icy bodies in the solar system - methane (CH4) and carbon dioxide (CO2). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 70 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  19. Light-absorbing aldol condensation products in acidic aerosols: Spectra, kinetics, and contribution to the absorption index

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; Esteve, William

    The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190-1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300-500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96-75 wt% H 2SO 4 solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of -(70±15) kJ mol -1 in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H 2SO 4 and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10 -4, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.

  20. Electronic absorption spectra of protonated pyrene and coronene in neon matrixes.

    PubMed

    Garkusha, Iryna; Fulara, Jan; Sarre, Peter J; Maier, John P

    2011-10-13

    Protonated pyrene and coronene have been isolated in 6 K neon matrixes. The cations were produced in the reaction of the parent aromatics with protonated ethanol in a hot-cathode discharge source, mass selected, and co-deposited with neon. Three electronic transitions of the most stable isomer of protonated pyrene and four of protonated coronene were recorded. The strongest, S(1) ← S(0) transitions, are in the visible region, with onset at 487.5 nm for protonated pyrene and 695.6 nm for protonated coronene. The corresponding neutrals were also observed. The absorptions were assigned on the basis of ab initio coupled-cluster and time-dependent density functional theory calculations. The astrophysical relevance of protonated polycyclic aromatic hydrocarbons is discussed. PMID:21861507

  1. Electron bubbles in liquid helium: Density functional calculations of infrared absorption spectra

    SciTech Connect

    Grau, Victor; Barranco, Manuel; Mayol, Ricardo; Pi, Marti

    2006-02-01

    Within density functional theory, we have calculated the energy of the transitions from the ground state to the first two excited states in the electron bubbles in liquid helium at pressures from zero to about the solidification pressure. For {sup 4}He at low temperatures, our results are in very good agreement with infrared absorption experiments. Above a temperature of {approx}2 K, we overestimate the energy of the 1s-1p transition. We attribute this to the break down of the Franck-Condon principle due to the presence of helium vapor inside the bubble. Our results indicate that the 1s-2p transition energies are sensitive not only to the size of the electron bubble, but also to its surface thickness. We also present results for the infrared transitions in the case of liquid {sup 3}He, for which we lack experimental data.

  2. Absorption spectra of Q 0000-263 and Q 1442+101

    NASA Technical Reports Server (NTRS)

    Frye, B. L.; Bechtold, J.; Moustakas, L. A.; Dobrzycki, A.

    1993-01-01

    Studying the Lyman-alpha forest allows us to trace the cosmological distribution of matter through time, and may reveal insights into important questions such as the onset of galaxy formation. An equation for determining the number of Lyman-alpha absorption lines per redshift per rest equivalent in the Lyman-alpha forest is given. For a nonevolving population of clouds gamma = 1 for q(sub 0) = 0, and gamma = 0.5 for q(sub 0) = 0.5. A detailed study of the Lyman-alpha forests of Q 1442+101 at z(sub em) = 3.54 and Q 0000-263 at z(sub em) = 4.11.

  3. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

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

    SciTech Connect

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

    2013-05-01

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

  7. Absorption spectra of rhodamine B dimers in dip-coated thin films prepared by the sol-gel method

    NASA Astrophysics Data System (ADS)

    Fujii, Tsuneo; Nishikiori, Hiromasa; Tamura, Takuma

    1995-02-01

    Thin films including rhodamine B (RB) which were dip-coated using the sol-gel reaction of tetraethyl orthosilicate (TEOS) have been prepared as a function of time and their absorption spectra observed 72 h after preparation of the thin films. One monomer and two dimers (H- and J-types) are clearly and simultaneously resolved both for RB in the thin films and the water-ethanol mixed solvent. Just after mixing the reaction system, the proportion of the dimers for RB was significant, and the H and J dimer amounts were nearly equal. As the sol-gel reaction proceeded, the relative contribution from the monomer species increased. The relative contribution of the monomer to that of the dimers reached a constant value long before the gelation time. This behavior indicates that the dye molecules are encapsulated in a certain structural region (pores) long before the gelation point of the sol-gel reaction of TEOS.

  8. Modeling of collision induced absorption spectra of CO2-CO2 pairs for planetary atmosphere of Venus

    NASA Technical Reports Server (NTRS)

    Borysow, Aleksandra

    1995-01-01

    The objective of the proposal was to model the rototranslational and rotovibrational collision induced absorption spectral bands of importance for the radiative transfer analysis of the atmosphere of Venus. Our main task has involved CO2 pairs. The approach is not straightforward: whereas computational techniques to compute CIA spectra of small linear molecules exist, and were successfully applied to molecules like H2 or N2, they fail when applied to large molecules like CO2. For small molecules one can safely assume that the interaction potential is isotropic. The same approximation does not work for CO2, and when employed, it gives an incorrect band shape and only 50 percent of the CIA intensity.

  9. FTIR spectrometer with 30 m optical cell and its applications to the sensitive measurements of selective and nonselective absorption spectra

    NASA Astrophysics Data System (ADS)

    Ponomarev, Yu. N.; Solodov, A. A.; Solodov, A. M.; Petrova, T. M.; Naumenko, O. V.

    2016-07-01

    A description of the spectroscopic complex at V.E. Zuev Institute of Atmospheric Optics, SB RAS, operating in a wide spectral range with high threshold sensitivity to the absorption coefficient is presented. Measurements of weak lines and nonselective spectra of CO2 and H2O were performed based on the built setup. As new application of this setup, positions and intensities of 152 weak lines of H2O were measured between 2400 and 2560 cm-1 with threshold sensitivity of 8.6×10-10 cm-1, and compared with available calculated and experimental data. Essential deviations between the new intensity measurements and calculated data accepted in HITRAN 2012 and GEISA 2015 forthcoming release are found.

  10. Sensitivity of absorption spectra to surface segregation in InGaN/GaN quantum well structures

    SciTech Connect

    Klymenko, M. V.; Shulika, O. V.; Sukhoivanov, I. A.

    2014-05-15

    We investigate the influence of the indium surface segregation on absorption spectra in InGaN/GaN quantum well structures having different indium amount. Results of the mathematical modeling show that such influence is more pronounced in quantum well structures with high indium amounts. The origin of this effect is related to the interplay between the indium surface segregation and internal electrostatic fields. Our theoretical analysis is performed using semiconductor Bloch equations within the Hartree-Fock approximation including into consideration excitonic effects. Results of the global sensitivity analysis evidence that the influence of the indium surface segregation is less than one order of magnitude in comparison with the impact of the quantum-well width and indium molar fraction. Also, the influence of the indium surface segregation is not the same for each interface of the quantum well.

  11. Detection of narrow C 4 and Si 4 absorption features in spectra of stars within 200 pc f the Sun

    NASA Technical Reports Server (NTRS)

    Molaro, P.; Beckman, J. E.; Franco, M.; Morossi, C.; Ramella, M.

    1984-01-01

    Detection of narrow (Beta lambda 0.5 A) absorption features in C 4 at lambda lambda 1548 and 1550 have been made in the spectra of 4 late B dwarfs within 200 pc of the Sun; the Si4 doublet at lambda lambda 1393 and 1403 shows up in two of them. It is argued that it is difficult to account for the strengths, widths, shapes, and C IV/Si IV ratios in terms consistent with a circumstellar origin except possibly for an asymmetric C IV component in one star (HD 185037). The most probable source is semi-torrid gas in the 50,000 K range forming the interfaces between cooler H 1 clouds and the ambient medium at coronal temperatures. Late B rapid rotators are used for local interstellar medium probing of this kind.

  12. Optical and infrared absorption spectra of 3d transition metal ions-doped sodium borophosphate glasses and effect of gamma irradiation

    NASA Astrophysics Data System (ADS)

    Abdelghany, A. M.; ElBatal, F. H.; Azooz, M. A.; Ouis, M. A.; ElBatal, H. A.

    2012-12-01

    Undoped and transition metals (3d TM) doped sodium borophosphate glasses were prepared. UV-visible absorption spectra were measured in the region 200-900 nm before and after gamma irradiation. Experimental optical data indicate that the undoped sodium borophosphate glass reveals before irradiation strong and broad UV absorption and no visible bands could be identified. Such UV absorption is related to the presence of unavoidable trace iron impurities within the raw materials used for preparation of this base borophosphate glass. The TMs-doped glasses show absorption bands within the UV and/or visible regions which are characteristic to each respective TM ion in addition to the UV absorption observed from the host base glass. Infrared absorption spectra of the undoped and TMs-doped glasses reveal complex FTIR consisting of extended characteristic vibrational bands which are specific for phosphate groups as a main constituent but with the sharing of some vibrations due to the borate groups. This criterion was investigated and approved using DAT (deconvolution analysis technique). The effects of different TMs ions on the FTIR spectra are very limited due to the low doping level (0.2%) introduced in the glass composition. Gamma irradiation causes minor effect on the FTIR spectra specifically the decrease of intensities of some bands. Such behavior is related to the change of bond angles and/or bond lengths of some structural building units upon gamma irradiation.

  13. [Fatty acid composition of phospholipids of erythrocytes of lamprey, frog, rat, and absorption spectra of their lipid extracts].

    PubMed

    Zabelinskii, S A; Chebotareva, M A; Shukolyukova, E P; Krivchenko, A I

    2014-01-01

    The work deals with study of content and fatty acid composition of phospholipids as well as of absorption spectra of lipid extracts of blood erythrocytes poikilothermal and homoiothermal animals of different evolutionary levels. Objects of study were poikilothermal lamprey (Lampetra fluviatilis) consuming oxygen from water and the common frog (Rana temporatia) consuming it both from water and from air. Homoiothermal animals were white rats (Rattus rattus) inhabiting in the air medium. The animals were studied at the winter-spring periods. There was established the twofold predominance of the phospholipid content in the lamprey plasma as compared with erythrocytes. In frog and rat the reverse ratio was observed. Based on study of the fatty acid composition of erythrocyte phospholipids it is suggested the higher density of membranes of lamprey as compared with frog membranes. As to fatty acides of the rat blood erythrocytic fraction, they turned out to be less diverse, with almost twofold predominance of saturated over unsaturated acids and not containing the long-chained (C22) Ω3 acids. All this leads to the low unsaturation index and, accordingly, to a dense packing of fatty acids in membrane structures of rat erythrocytes. Mechanism of reversible binding of O2 molecules by hemoglobin in erythrocytes is discussed. The mechanism of interaction of O2 molecules with water molecules is likely to interfere with exchange interaction electrons of hemoglobin iron atoms and oxygen molecule. This confirms our obtained absorption spectra showing that in the lipid extract practically not containing water the heme isolated from erythrocytes is converted to hemin. PMID:25775862

  14. Electronic absorption spectra and solvatochromic shifts by the vertical excitation model: solvated clusters and molecular dynamics sampling.

    PubMed

    Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

    2015-01-22

    A physically realistic treatment of solvatochromic shifts in liquid-phase electronic absorption spectra requires a proper account for various short- and long-range equilibrium and nonequilibrium solute-solvent interactions. The present article demonstrates that such a treatment can be accomplished using a mixed discrete-continuum approach based on the two-time-scale self-consistent state-specific vertical excitation model (called VEM) for electronic excitation in solution. We apply this mixed approach in combination with time-dependent density functional theory to compute UV/vis absorption spectra in solution for the n → π* ((1)A2) transition for acetone in methanol and in water, the π → π* ((1)A1) transition for para-nitroaniline (PNA) in methanol and in water, the n → π* ((1)B1) transition for pyridine in water, and the n → π* ((1)B1) transition for pyrimidine in water. Hydrogen bonding and first-solvation-shell-specific complexation are included by means of explicit solvent molecules, and solute-solvent dispersion is included by using the solvation model with state-specific polarizability (SMSSP). Geometries of microsolvated clusters were treated in two different ways, (i) using single liquid-phase global-minimum solute-solvent clusters containing up to two explicit solvent molecules and (ii) using solute-solvent cluster snapshots derived from molecular dynamics (MD) trajectories. The calculations in water involve using VEM/TDDFT excitation energies and oscillator strengths computed over 200 MD-derived solute-solvent clusters and convoluted with Gaussian functions. We also calculate ground- and excited-state dipole moments for interpretation. We find that inclusion of explicit solvent molecules generally improves the agreement with experiment and can be recommended as a way to include the effect of hydrogen bonding in solvatochromic shifts. PMID:25159827

  15. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

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

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

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

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

    SciTech Connect

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

    2008-02-16

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

  18. Bounds on the fine structure constant variability from Fe ii absorption lines in QSO spectra

    NASA Astrophysics Data System (ADS)

    Molaro, P.; Reimers, D.; Agafonova, I. I.; Levshakov, S. A.

    2008-10-01

    The Single Ion Differential α Measurement (SIDAM)method for measuring Δα/α and its figures of merit are illustrated together withthe results produced by means of Fe ii absorption linesof QSO intervening systems. The method providesΔα/α = -0.12 ±1.79 ppm (parts-per-million) at zabs = 1.15towards HE 0515-4414 and Δα/α = 5.66±2.67 ppm at zabs = 1.84towards Q 1101-264, which are so far the most accurate measurementsfor single systems. SIDAM analysis for 3 systems from the Chand et al. [1]sample provides inconsistent results which we interpret as due tocalibration errors of the Chand et al. data at the level ≈10 ppm.In one system evidence for photo-ionization Dopplershift between Mg ii and Fe ii lines is found.This evidence has important bearings on the Many Multipletmethod where the signal for Δα/αvariabilityis carried mainly by systems involving Mg ii absorbers.Some correlations are also found in the Murphy et al. [10] sample which suggestlarger errors than previously reported.Thus, we consider unlikely that both the Chand et al.and Murphy et al. datasets could providean estimate of Δα/α with an accuracy at the level of 1 ppm.A new spectrograph like the ESPRESSO projectwill be crucial to make progress in the astronomical determination of Δα/α.

  19. Dressing effects in the attosecond transient absorption spectra of doubly excited states in helium

    NASA Astrophysics Data System (ADS)

    Argenti, L.; Jiménez-Galán, Á.; Marante, C.; Ott, C.; Pfeifer, T.; Martín, F.

    2015-06-01

    Strong-field manipulation of autoionizing states is a crucial aspect of electronic quantum control. Recent measurements of the attosecond transient absorption spectrum (ATAS) of helium dressed by a few-cycle visible pulse [C. Ott et al., Nature (London) 516, 374 (2014), 10.1038/nature14026] provide evidence of the inversion of Fano profiles. With the support of accurate ab initio calculations that reproduce the results of the latter experiment, here we investigate the new physics that arise from ATAS when the laser intensity is increased. In particular, we show that (i) previously unnoticed signatures of the dark 2 p21S doubly excited state are observed in the experimental spectrum, (ii) inversion of Fano profiles is predicted to be periodic in the laser intensity, and (iii) the ac Stark shift of the higher terms in the s p2,n + autoionizing series exceeds the ponderomotive energy, which is the result of a genuine two-electron contribution to the polarization of the excited atom.

  20. New aspects concerning the energy transfer in carotenoids by measuring intracavity absorption spectra and delayed fluorescence

    NASA Astrophysics Data System (ADS)

    Bettermann, Hans; Bouschen, Werner; Ulrich, Lars; Domnick, Gabriele; Martin, H. D.

    1999-05-01

    The first excited singlet state and the lower energetic triplet states of carotenoids are considered to be involved in the light-harvesting as well as in the photochemical protection of cells, respectively. For this reason, the symmetry-forbidden S 0-S 1 (1 1A g-2 1A g) transitions and the multiplicity-forbidden S 0-T 2 (1 1A g-2 3A g) transition of the model carotenoid 8,13-dimethyl-2,2,19,19-tetramethoxy-icosa-4,6,8,10,12,14,16-heptaene-3,18-dione were investigated by intracavity absorption spectroscopy from low-concentrated ethanolic solutions. Both transitions are shaped by promoting modes caused by Herzberg-Teller coupling and the sequence of these modes allows the precise determination of the non-visible S 0-S 1 (0-0)- and S 0-T 2 (0-0)-transitions. The assignments of the singlet-triplet transitions were additionally supported by measuring delayed fluorescence from crystalline samples by directly exciting vibronic triplet states. The vibronic coupling is promoted by C-H bending vibrations of the chain and mainly by deformation modes of the terminating groups of the carotenoid.