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Sample records for absorption spectra fluorescence

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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).

  6. 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).

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Data of fluorescence, UV-vis absorption and FTIR spectra for the study of interaction between two food colourants and BSA.

    PubMed

    Li, Tian; Cheng, Zhengjun; Cao, Lijun; Jiang, Xiaohui; Fan, Lei

    2016-09-01

    In this data article, the fluorescence, UV-vis absorption and FTIR spectra data of BSA-AR1/AG50 system were presented, which were used for obtaining the binding characterization (such as binding constant, binding distance, binding site, thermodynamics, and structural stability of protein) between BSA and AR1/AG50. PMID:27508228

  18. Solvent Effects on the Electronic Absorption and Fluorescence Spectra of HNP: Estimation of Ground and Excited State Dipole Moments.

    PubMed

    Desai, Vani R; Hunagund, Shirajahammad M; Basanagouda, Mahantesha; Kadadevarmath, Jagadish S; Sidarai, Ashok H

    2016-07-01

    We report the effect of solvents on absorption and fluorescence spectra of biologically active 3(2H)-pyridazinone namely 5-(2-hydroxy-naphthalen-1-yl)-2-phenyl-2H-pyridazin-3-one (HNP) in different solvents at room temperature. The ground and the excited state dipole moments of HNP molecule was estimated from Lippert's, Bakshiev's and Kawski-Chamma-Viallet's equations using the solvatochromic shift method. The ground state dipole moment (μ g ) was also estimated by Guggenheim and Higasi method using the dielectric constant and refractive index of solute at different concentrations, the μ g value obtained from these two methods are comparable to the μ g value obtained by the solvatochromic shift method. The excited state dipole moment (μ e ) is greater than the ground state dipole moment (μ g ), which indicates that the excited state is more polar than the ground state. Further, we have evaluated the change in dipole moment (Δμ) from the solvatochromic shift method and on the basis of molecular-microscopic solvent polarity parameter[Formula: see text], later on the values were compared. PMID:27220623

  19. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    PubMed

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-01

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  20. Monomeric C-phycocyanin at room temperature and 77 K. Resolution of the absorption and fluorescence spectra of the individual chromophores and the energy-transfer rate constants

    SciTech Connect

    Debreczeny, M.P.; Sauer, K. Univ. of California, Berkeley, CA ); Zhou, J.; Bryant, D.A. )

    1993-09-23

    At both room temperature (RT) and 77 K, the absorption and fluorescence spectra of the three individual chromophore types ([alpha][sub 84], [beta][sub 84], and [beta][sub 155]) found in monomeric C-phycocyanin ([alpha][sup PC][beta][sup PC]), isolated from the cyanobacterium Synechococcus sp. PCC 7002, were resolved along with the rates of energy transfer between the chromophores. The cpcB/C155S mutant, whose PC is missing the [beta][sub 155] chromophore, was useful in effecting this resolution. At RT, the single broad peak in the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) was resolved into its three-component spectra by comparing the steady-state absorption spectra of the isolated wild-type [alpha] subunit of PC ([alpha][sup PC]) (containing only the [alpha][sub 84] chromophore) with those of the monomeric PCs isolated from the mutant strain ([alpha][sup PC][beta]*) and the wild-type strain ([alpha][sup PC][beta][sup PC]). At 77 K, the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) splits into two peaks. This partial resolution at 77 K of the chromophore spectra of ([alpha][sup PC][beta][sup PC]) when compared with the 77 K absorption spectra of [alpha][sup PC], [beta][sup PC], and ([alpha][sup PC][beta]*) provided a confirmation of our RT assignments of the chromophore absorption spectra. 38 refs., 9 figs., 6 tabs.

  1. Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

    NASA Astrophysics Data System (ADS)

    Ten, G. N.; Kadrov, D. M.; Berezin, M. K.; Baranov, V. I.

    2014-11-01

    We have calculated vibronic spectra of the first electronic nπ* transitions of pyridine and pyrimidine in the isolated state using the DFT method in the Franck-Condon approximation. Vibrational spectra for the ground and excited states have been calculated in the anharmonic approximation, which allowed us to refine the assignment of normal vibrations of pyridine and pyrimidine. We have done a complete interpretation of the vibrational structure of the absorption and fluorescence spectra of pyridine and pyrimidine. It has been shown that Fermi resonances between fundamental and combination vibrations and overtones 12 and 16 b + 4, 6 a and 2 × 16 b affect the formation of the vibrational structure of electronic spectra of pyrimidine. Good agreement between calculated and experimental spectra confirms the correctness of the models of the two molecules in their ground and excited states, which makes it possible to use the models in further investigations of various properties of these molecules in electronically excited states, e.g., tautomerism of pyrimidine bases of nucleic acids.

  2. [Characteristics of absorption and fluorescence spectra of dissolved organic matter from confluence of rivers: case study of Qujiang River-Jialing River and Fujiang River-Jialing River].

    PubMed

    Yan, Jin-Long; Jiang, Tao; Gao, Jie; Wei, Shi-Qiang; Lu, Song; Liu, Jiang

    2015-03-01

    Three-dimensional fluorescence spectroscopy combined with ultraviolet-visible (UV-Vis) absorption spectra was used to investigate the change characteristics of dissolved organic matter (DOM) in confluences water of Qujiang River-Jialing River and Fujiang River-Jialing River, respectively. The results suggested that DOM showed a significant terrestrial input signal in all the sampling sites, FI < 1.4, HIX > 0.8, possibly representing remarkable signals of humus resulted from humic-like component. Moreover, the mixing zone of this study showed a non-conservative mixed behavior, which had a limited contribution, and was not the dominant factor to interpret the change characteristics of DOM in confluences zones. Different land-use types along all the rivers had an obvious impact on DOM inputs. Results of cluster analysis showed that a higher degree of aromaticity and humification components was observed as the predominant contributor to DOM when the land-use type was forest and farmland ecosystem, for example the confluences of Qujiang River-Jialing River. On the other hand, high concentrations of DOM with relative simple structures were found in the water when the urban land-use type was predominant, for example the confluences of Fujiang River-Jialing River. Meanwhile, a new fluorescent signal of protein-like components (peak T) appeared, which manifested a significant effect on the water quality resulted from anthropogenic activities. PMID:25929053

  3. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    SciTech Connect

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan; Kim, Sunghwan

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  4. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Basavaraja, Jana; Suresh Kumar, H. M.; Inamdar, S. R.; Wari, M. N.

    2016-02-01

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π → π* transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μe). It is observed that dipole moment value of excited state (μe) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state.

  5. Comparison of Synchrotron X-Ray Fluorescence Mapping and Micro-XANES to Bulk X-Ray Absorption Spectra in Metal-Contaminated Sediments

    SciTech Connect

    O'Day, P; Carroll, S A; Bajt, S

    2003-01-16

    Synchrotron X-ray absorption spectroscopy (XAS) is one of the few techniques that can supply molecular-scale information for a variety of elements at concentrations relevant to natural systems in non-vacuum conditions. Bulk XAS analysis supplies the dominant chemical bonding mode(s) for a specific element. In complex materials such as natural soils and sediments, however, the dominant mode may not necessarily be the most reactive because changes in speciation at surfaces may results in changes in reactivity. Our previous work at Naval Air Station (NAS) Alameda (CA) focused on in situ metal chemistry in surface and deep sediments, and the impact of metal mobility by sediment oxidation. Estuary sediments at the Alameda Naval Station Air in California have elevated metal concentrations that increase with increasing depth. The metal concentrations in these sediments are: Cd (10-350 ppm), Cr (200-1000 ppm), Cu (100-230 ppm), Pb (200-1200 ppm) and Zn (250-600 ppm). We have extensively characterized these sediments using bulk XAS and other non-synchrotron supporting methods [ 1]. In this experiment, we collected fluorescence element maps using synchrotron X-ray microprobe of unreacted and seawater-oxidized sediment samples from Alameda NAS to determine the spatial distribution and correlation of lead, zinc, and iron. We then compared micro-XANES spectra for lead and zinc collected with the X-ray microprobe to previously collected bulk XANES spectra. The results from our bulk XAS characterization of the sediments showed both oxide and sulfide components for the trace metals. However, the bulk XAS data were not able to identify the composition of the oxide component (i.e. carbonate or hydroxide), nor could absorbed species or solid solutions be definitively identified. Our objective in using micro-XANES and fluorescence element maps was to attempt a more precise identification of metal speciation in or on individual particles.

  6. Absorption and fluorescence spectroscopy on a smartphone

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Arafat; Canning, John; Cook, Kevin; Ast, Sandra; Rutledge, Peter J.; Jamalipour, Abbas

    2015-07-01

    A self-powered smartphone-based field-portable "dual" spectrometer has been developed for both absorption and fluorescence measurements. The smartphone's existing flash LED has sufficient optical irradiance to undertake absorption measurements within a 3D-printed case containing a low cost nano-imprinted polymer diffraction grating. A UV (λex ~ 370 nm) and VIS (λex ~ 450 nm) LED are wired into the circuit of the flash LED to provide an excitation source for fluorescence measurements. Using a customized app on the smartphone, measurements of absorption and fluorescence spectra are demonstrated using pH-sensitive and Zn2+-responsive probes. Detection over a 300 nm span with 0.42 nm/pixel spectral resolution is demonstrated. Despite the low cost and small size of the portable spectrometer, the results compare well with bench top instruments.

  7. Gritty Surface Sample Holder Invented To Obtain Correct X-ray Absorption Fine Structure Spectra for Concentrated Materials by Fluorescence Yield.

    PubMed

    Abe, Hitoshi; Niwa, Yasuhiro; Kimura, Masao; Murakami, Youichi; Yokoyama, Toshiharu; Hosono, Hideo

    2016-04-01

    A gritty surface sample holder has been invented to obtain correct XAFS spectra for concentrated samples by fluorescence yield (FY). Materials are usually mixed with boron nitride (BN) to prepare proper concentrations to measure XAFS spectra. Some materials, however, could not be mixed with BN and would be measured in too concentrated conditions to obtain correct XAFS spectra. Consequently, XAFS spectra will be incorrect typically with decreased intensities of the peaks. We have invented the gritty surface sample holders to obtain correct XAFS spectra even for concentrated materials for FY measurements. Pure Cu and CuO powders were measured mounted on the sample holders, and the same spectra were obtained as transmission spectra of properly prepared samples. This sample holder is useful to measure XAFS for any concentrated materials. PMID:26978034

  8. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X {sup 1}A{sub g} ↔ A{sup 1}B{sub 1u} absorption and fluorescence spectra of perylene

    SciTech Connect

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

    2014-08-28

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

  9. Experimental and theoretical comparison between absorption, total electron yield, and fluorescence spectra of rare-earth M{sub 5} edges

    SciTech Connect

    Pompa, M.; Flank, A.M.; Lagarde, P.; Rife, J.C.; Stekhin, I.; Nakazawa, M.; Ogasawara, H.; Kotani, A.

    1997-07-01

    Besides the now well-known self-absorption effect, several phenomena related to the multiplet structure of the intermediate state may occur which render x-ray fluorescence different from the true absorption in 3d transition metals at the L edge and at the M{sub 4,5} edges of rare earths. Special selection rules of the radiative de-excitation process play an important role there. We have measured the absorption coefficient of thin films of lanthanum, samarium, and thulium deposited on an aluminum foil, at room temperature, through the simultaneous detection of the transmission, total electron yield, and 150-eV bandwidth fluorescence yield. The latter result shows differences as compared to the other two, and exhibits polarization effects depending upon the angle between incident and outgoing photons. The resonant x-ray fluorescence spectrum is calculated using an atomic model, and then integrated over the emitted energy, to predict the fluorescence yield spectrum. Very good agreement is obtained between the theory and experiment. {copyright} {ital 1997} {ital The American Physical Society}

  10. Towards the understanding at the molecular level of the structured-water absorption and fluorescence spectra: a fingerprint of π-stacked water

    NASA Astrophysics Data System (ADS)

    Segarra-Martí, Javier; Coto, Pedro B.; Rubio, Mercedes; Roca-Sanjuán, Daniel; Merchán, Manuela

    2013-07-01

    An intriguing absorption peak around ∼270 nm (4.59 eV) has been recurrently recorded in aqueous solutions of salts, sugars, amino acids, in the free-solute zone (exclusion zone) adjacent to various hydrophilic surfaces, as well as a transient in the conversion process of ice to water. The corresponding associated fluorescence has been observed in the interval 480-490 nm (2.58-2.53 eV). The spectroscopic features have been related to the presence of structured water but its nature remains incompletely understood. On the basis of high-level ab initio computations, the main absorption feature of structured water is assigned to the presence of two π-stacked ground-state water molecules, preferably non-hydrogen bonded, at relatively short intermolecular distances (around 2 Å). The lowest singlet excited state is characterised by an equilibrium distance of around 2 Å with a vertical absorption transition predicted at 4.5 eV. The excited π-stacked dimer has a large binding energy (∼1 eV). Therefore, near-ultraviolet light may favour the formation of structured water. Two relaxed side-hydrated π-stacked water molecules (a relaxed tetramer) constitute the smallest unique excimer-type fluorescent moiety consistent with the available experimental data.

  11. 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

  12. 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.

  13. 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

  14. Fluorescence spectra shape based dynamic thermometry

    NASA Astrophysics Data System (ADS)

    Liu, Liwang; Creten, Sebastiaan; Firdaus, Yuliar; Agustin Flores Cuautle, Jose Jesus; Kouyaté, Mansour; Van der Auweraer, Mark; Glorieux, Christ

    2014-01-01

    An entirely optical, dynamic thermometry technique based on the temperature dependence of a fluorescence spectrum is presented. Different from conventional intensity-based fluorescence thermometry, in this work, neural network recognition is employed to extract the sample temperature from the magnitude and shape of recorded fluorescence spectra. As a demonstration to determine the depth profile of dynamical temperature variations and of the thermal and optical properties of semitransparent samples, in-depth photothermally induced periodical temperature oscillations of a rhodamine B and copper chloride dyed glycerol sample were measured with an accuracy of 4.2 mK.Hz-1/2 and fitted well by a 1D thermal diffusion model.

  15. 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.

  16. Research on fluorescence spectra of cancer blood

    NASA Astrophysics Data System (ADS)

    Liu, Kunxiang; He, Wenliang; Zhao, Wenyan; Liu, Ying

    2007-11-01

    The fluorescence spectral characteristic of tumor blood was studied by laser-induced fluorescence technology, and compared with the fluorescence spectra of the same type healthy mice blood, the differences between them are distinct. When the whole blood solutions were induced by 407nm laser, they radiate fluorescence band from 420nm to 750 nm, which spectral peak located at 620nm. In high concentration solutions (blood concentration is higher than 4%), the fluorescence intensity are lower than normal blood, but in those low concentration solutions (blood concentration is lower than 2%) the fluorescence intensity of the tumor blood are higher than the normal ones. It is analyzed that the change of the fluorescence characteristic between the tumor blood and the normal is caused by the concentration difference of the tumor identification-porphyrin. The experimental results showed that the obvious difference of the fluorescence spectral characteristic between the forepart tumor and normal blood can offer some value assistance to clinical diagnosis on cancer.

  17. 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

  18. A new highly selective, ratiometric and colorimetric fluorescence sensor for Cu(2+) with a remarkable red shift in absorption and emission spectra based on internal charge transfer.

    PubMed

    Goswami, Shyamaprosad; Sen, Debabrata; Das, Nirmal Kumar

    2010-02-19

    A new 1,8-diaminonaphthalene based ratiometric and highly selective colorimetric "off-on" type of fluorescent probe, receptor 2 has been designed and synthesized that senses only Cu(2+) among the other heavy and transition metal ions examined on the basis of internal charge transfer (ICT). The visual sensitivity of the receptor 2 is remarkable, showing dual color changes from colorless (receptor) to purple followed by blue and a large red shift in emission upon Cu(2+) complexation. PMID:20104900

  19. 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.

  20. The Taser Induced Fluorescence Spectra And Decay Lifetime Of NI2+ Doped Chrysoberyl

    NASA Astrophysics Data System (ADS)

    Hanting, Ji; Genwang, Wen; Jun, Oian; Zhende, Chen; Wenbin, Gao; Songhao, Lui

    1985-12-01

    This paper reports the experimental results on the fluorescence spectra and decay lifetime of 3T2---3A2 vibronic transition of NI2+ : BeAl204 with LIFM. The center wavelength of fluorescence spectra is 1.33u , the bandwidth (FWHM) is 0.14u (1.26 - 1.40u), and the center red-shift of fluorescence spectra in relative to absorption spectra is 0.225u at room temperature (300k). The radiation lifetime is 3T2 band is 198 us.

  1. Removing The Instrument Function From Fluorescence Spectra

    NASA Astrophysics Data System (ADS)

    Childs, Andrew F.

    1989-05-01

    The spectrum acquired at the sample phototnultiplier tube of a fluorescence spectrophotometer is a product of the sample spectrum and the instrument function. The determination of the instrument function and its removal from the acquired spectrum is often critical to the accurate determination of the physical properties of the sample. Methods are discussed for the determination and removal of the instrument function from excitation and emission spectra. Methods considered include quantum counters and ratio circuits for excitation correction, and emission correction against calibrated excitation systems, calibrated tungsten lamps, and NBS standard quinine sulfate.

  2. 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.

  3. 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.

  4. 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

  5. Solvent-induced multicolour fluorescence of amino-substituted 2,3-naphthalimides studied by fluorescence and transient absorption measurements.

    PubMed

    Fujii, Mayu; Namba, Misa; Yamaji, Minoru; Okamoto, Hideki

    2016-07-01

    A series of amino-2,3-naphthalimide derivatives having the amino functionality at 1-, 5- and 6-positions (, and , respectively) were prepared, and their photophysical properties were systematically investigated based on the measurements of steady-state absorption and fluorescence spectra, fluorescence lifetimes as well as transient absorption spectra. The s efficiently fluoresced in solution, and the emission spectra appreciably shifted depending on the solvent polarity. displayed only a slight fluorescence red-shift upon increasing the solvent polarity. In contrast, and showed marked positive solvatofluorochromism with large Stokes shifts displaying multicolour fluorescence; the fluorescence colours of and varied from violet-blue in hexane to orange-red in methanol. and , thus, serve as micro-environment responding fluorophores. In methanol, the intensity of the fluorescence emission band of and significantly reduced. Based on the fluorescence quantum yields and lifetimes, and transient absorption measurements, it has been revealed that internal conversion from the S1 state of s to the ground state was accelerated by the protic medium, resulting in a reduction in their fluorescence efficiency, while intersystem crossing from the S1 state to a triplet state was not responsible for the decrease of fluorescence intensity. PMID:27251860

  6. Fluorescence excitation spectra of all-trans-1,6-diphenylhexatriene conformers: Adiabatic conformer equilibration in the 21Ag state

    NASA Astrophysics Data System (ADS)

    Turek, Andrzej M.; Krishna, Tallapragada S. R.; Brela, Mateusz; Saltiel, Jack

    2016-03-01

    Fluorescence spectra of all-trans-1,6-diphenyl-1,3,5-hexatriene were measured in n-hexadecane at 99 °C by varying λexc in the 294-404 nm range. Resolution of this spectral matrix into s-trans,s-trans and s-cis,s-trans conformer fluorescence spectra yields the λexc dependence of fractional contributions which are converted to conformer specific fluorescence excitation spectra. Conformer absorption spectra obtained from the fluorescence excitation spectra are remarkably similar, but differ significantly from absorption spectra derived from a spectrothermal absorption spectral matrix measured in n-alkanes under isopolarizability conditions. The results reveal substantial conformer equilibration in the excited state. Theory is consistent with adiabatic conformer equilibration in the 21Ag state.

  7. Photoadaptation in marine phytoplankton: changes in spectral absorption and excitation of chlorophyll a fluorescence

    SciTech Connect

    Neori, A.; Holm-Hansen, O.; Mitchell, B.G.; Kiefer, D.A.

    1984-10-01

    The optical properties of marine phytoplankton were examined by measuring the absorption spectra and fluorescence excitation spectra of chlorophyll a for natural marine particles collected on glass fiber filters. Samples were collected at different depths from stations in temperate waters of the Southern California Bight and in polar waters of the Scotia and Ross Seas. At all stations, phytoplankton fluorescence excitation and absorption spectra changed systematically with depth and vertical stability of the water columns. In samples from deeper waters, both absorption and chlorophyll a fluorescence excitation spectra showed enhancement in the blue-to-green portion of the spectrum (470-560 nm) relative to that at 440 nm. Since similar changes in absorption and excitation were induced by incubating sea water samples at different light intensities, the changes in optical properties can be attributed to photoadaptation of the phytoplankton. The data indicate that in the natural populations studied, shade adaptation caused increases in the concentration of photosynthetic accessory pigments relative to chlorophyll a. These changes in cellular pigment composition were detectable within less than 1 day. Comparisons of absorption spectra with fluorescence excitation spectra indicate an apparent increase in the efficiency of sensitization of chlorophyll a fluorescence in the blue and green spectral regions for low light populations. 30 references, 6 figures.

  8. 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.

  9. Absorption and fluorescent spectral studies of imidazophenazine derivatives.

    PubMed

    Ryazanova, O A; Zozulya, V N; Voloshin, I M; Karachevtsev, V A; Makitruk, V L; Stepanian, S G

    2004-07-01

    Absorption and fluorescent spectra as well as fluorescence polarization degree of imidazo-[4,5-d]-phenazine (F1) and its two modified derivatives, 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F2) and 1,2,3-triazole-[4,5-d]-phenazine (F3), were investigated in organic solvents of various polarities and hydrogen bonding abilities. Extinction coefficients of F2 and F3 are increased, their fluorescence Stokes shifts are reduced in comparison with those for unmodified imidazophenazine. For F3 a red shift of the longwave absorption band is observed by 15-20 nm. Modifications of imidazophenazine have led to a sufficient increase of fluorescence polarization degrees that enables to use F2 and F3 as promising fluorescent probes with polarization method application. The configuration, atomic charge distribution and dipole moments of the isolated dye molecules in the ground state were calculated by the DFT method. The computation has revealed that ground state dipole moments of F1, F2, and F3 differ slightly and are equal to 3.5, 3.2, and 3.7D, respectively. The changes in dipole moments upon the optical excitation for all derivatives estimated using Lippert equation were found to be Deltamu = 9 D. The energies of the electronic S1<--S0 transition in solvents of different proton donor abilities were determined, and energetic diagram illustrating the substituent effect was plotted. For nucleoside analogs of these compounds, covalently incorporated into a nucleotide chain, we have considered a possibility to use them as fluorescent reporters of hybridization of antisense oligonucleotides, as well as molecular anchors for its stabilization. PMID:15248979

  10. DNA-Dye-Conjugates: Conformations and Spectra of Fluorescence Probes

    PubMed Central

    Beierlein, Frank R.; Paradas Palomo, Miguel; Sharapa, Dmitry I.; Zozulia, Oleksii; Mokhir, Andriy; Clark, Timothy

    2016-01-01

    Extensive molecular-dynamics (MD) simulations have been used to investigate DNA-dye and DNA-photosensitizer conjugates, which act as reactants in templated reactions leading to the generation of fluorescent products in the presence of specific desoxyribonucleic acid sequences (targets). Such reactions are potentially suitable for detecting target nucleic acids in live cells by fluorescence microscopy or flow cytometry. The simulations show how the attached dyes/photosensitizers influence DNA structure and reveal the relative orientations of the chromophores with respect to each other. Our results will help to optimize the reactants for the templated reactions, especially length and structure of the spacers used to link reporter dyes or photosensitizers to the oligonucleotides responsible for target recognition. Furthermore, we demonstrate that the structural ensembles obtained from the simulations can be used to calculate steady-state UV-vis absorption and emission spectra. We also show how important quantities describing the quenching of the reporter dye via fluorescence resonance energy transfer (FRET) can be calculated from the simulation data, and we compare these for different relative chromophore geometries. PMID:27467071

  11. 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.

  12. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

    SciTech Connect

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2013-05-10

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Experimental recovery of intrinsic fluorescence and fluorophore concentration in the presence of hemoglobin: spectral effect of scattering and absorption on fluorescence

    NASA Astrophysics Data System (ADS)

    Du Le, Vinh Nguyen; Patterson, Michael S.; Farrell, Thomas J.; Hayward, Joseph E.; Fang, Qiyin

    2015-12-01

    The ability to recover the intrinsic fluorescence of biological fluorophores is crucial to accurately identify the fluorophores and quantify their concentrations in the media. Although some studies have successfully retrieved the fluorescence spectral shape of known fluorophores, the techniques usually came with heavy computation costs and did not apply for strongly absorptive media, and the intrinsic fluorescence intensity and fluorophore concentration were not recovered. In this communication, an experimental approach was presented to recover intrinsic fluorescence and concentration of fluorescein in the presence of hemoglobin (Hb). The results indicated that the method was efficient in recovering the intrinsic fluorescence peak and fluorophore concentration with an error of 3% and 10%, respectively. The results also suggested that chromophores with irregular absorption spectra (e.g., Hb) have more profound effects on fluorescence spectral shape than chromophores with monotonic absorption and scattering spectra (e.g., black India ink and polystyrene microspheres).

  19. 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.

  20. 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.

  1. Understanding the contributions of NADH and collagen to cervical tissue fluorescence spectra: modeling, measurements, and implications

    NASA Astrophysics Data System (ADS)

    Drezek, Rebekah A.; Sokolov, Konstantin V.; Utzinger, Urs; Boiko, Iouri; Malpica, Anais; Follen, Michele; Richards-Kortum, Rebecca R.

    2001-10-01

    Objective: At 380 nm excitation, cervical tissue fluorescence spectra demonstrate characteristic changes with both patient age and the presence of dysplasia. A Monte Carlo model was developed in order to quantitatively examine how intrinsic NADH and collagen fluorescence, in combination with tissue scattering and absorption properties, yield measured tissue spectra. Methods: Excitation-emission matrices were measured for live cervical cells and collagen gel phantoms. Fluorescence microscopy of fresh tissue sections was performed to obtain the location and density of fluorophores as a function of patient age and the presence of dysplasia. A Monte Carlo model was developed which incorporated measurements of fluorophore line shapes and spatial distributions. Results: Modeled spectra were consistent with clinical measurements and indicate that an increase in NADH fluorescence and decrease in collagen fluorescence create clinically observed differences between normal and dysplastic tissue spectra. Model predictions were most sensitive to patient age and epithelial thickness. Conclusions: Monte Carlo techniques provide an important means to investigate the combined contributions of multiple fluorophores to measured emission spectra. The approach will prove increasingly valuable as a more sophisticated understanding of in vivo optical properties is developed.

  2. 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.

  3. 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.

  4. 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.

  5. Accurate modeling of fluorescence line narrowing difference spectra: Direct measurement of the single-site fluorescence spectrum

    NASA Astrophysics Data System (ADS)

    Reppert, Mike; Naibo, Virginia; Jankowiak, Ryszard

    2010-07-01

    Accurate lineshape functions for modeling fluorescence line narrowing (FLN) difference spectra (ΔFLN spectra) in the low-fluence limit are derived and examined in terms of the physical interpretation of various contributions, including photoproduct absorption and emission. While in agreement with the earlier results of Jaaniso [Proc. Est. Acad. Sci., Phys., Math. 34, 277 (1985)] and Fünfschilling et al. [J. Lumin. 36, 85 (1986)], the derived formulas differ substantially from functions used recently [e.g., M. Rätsep et al., Chem. Phys. Lett. 479, 140 (2009)] to model ΔFLN spectra. In contrast to traditional FLN spectra, it is demonstrated that for most physically reasonable parameters, the ΔFLN spectrum reduces simply to the single-site fluorescence lineshape function. These results imply that direct measurement of a bulk-averaged single-site fluorescence lineshape function can be accomplished with no complicated extraction process or knowledge of any additional parameters such as site distribution function shape and width. We argue that previous analysis of ΔFLN spectra obtained for many photosynthetic complexes led to strong artificial lowering of apparent electron-phonon coupling strength, especially on the high-energy side of the pigment site distribution function.

  6. 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…

  7. Discrimination of phytoplankton classes using characteristic spectra of 3D fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Zhang, Qian-Qian; Lei, Shu-He; Wang, Xiu-Lin; Wang, Lei; Zhu, Chen-Jian

    2006-02-01

    The discrimination of phytoplankton classes using the characteristic fluorescence spectra extracted from three-dimensional fluorescence spectra was investigated. Single species cultures of 11 phytoplankton species, representing 5 major phytoplankton divisions, were used. The 3D fluorescence spectra of the cultures grown at different temperatures (20 and 15 °C) and illumination intensities (140, 80 and 30 μM m -2 s -1) were measured and their feature extraction methods were explored. Ordering Rayleigh and Raman scattering data as zero, the obtained excitation-emission matrices were processed by both singular value decomposition (SVD) and trilinear decomposition methods. The resulting first principal component can be regarded as the characteristic spectrum of the original 3D fluorescence spectrum. The analysis shows that such characteristic spectra have a discriminatory capability. At different temperatures, the characteristic spectra of Isochrysis galbana, Platymonas helgolanidica and Skeletonema costatuma have high degrees of similarity to their own species samples, while the spectra similarities of Alexandrium tamarense, Prorocentrum dentatum, Pseudo-nitzschia pungens, Chaetoceros curvisetus, Ch. Debilis, Ch. Didymus and Synechococcus sp. are not as significant as the other three species. C. curvisetus, Ch. Debilis and Ch. Didymus, belonging to genus Chaetoceros, have identical spectra and cannot be discriminated at all. Regarding all six diatom species as one class, the average discriminant error rate is below 9%. It is worth mentioning that the diatom class can be distinguished from A. tamarense and P. dentatum, which belong to Dinophyta.

  8. 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.

  9. Spectral signatures of fluorescence and light absorption to identify crude oils found in the marine environment

    NASA Astrophysics Data System (ADS)

    Baszanowska, E.; Otremba, Z.

    2014-08-01

    To protect the natural marine ecosystem, it is necessary to continuously enhance knowledge of environmental contamination, including oil pollution. Therefore, to properly track the qualitative and quantitative changes in the natural components of seawater, a description of the essential spectral features describing petroleum products is necessary. This study characterises two optically-different types of crude oils (Petrobaltic and Romashkino) - substances belonging to multi-fluorophoric systems. To obtain the spectral features of crude oils, the excitation-emission spectroscopy technique was applied. The fluorescence and light absorption properties for various concentrations of oils at a stabilised temperature are described. Both excitation-emission spectra (EEMs) and absorption spectra of crude oils are discussed. Based on the EEM spectra, both excitation end emission peaks for the wavelengthindependent fluorescence maximum (Exmax/ Emmax) - characteristic points for each type of oil - were identified and compared with the literature data concerning typical marine chemical structures.

  10. Fluorescence2D: Software for Accelerated Acquisition and Analysis of Two-Dimensional Fluorescence Spectra

    PubMed Central

    Kovrigin, Evgenii L.

    2014-01-01

    The Fluorescence2D is free software that allows analysis of two-dimensional fluorescence spectra obtained using the accelerated “triangular” acquisition schemes. The software is a combination of Python and MATLAB-based programs that perform conversion of the triangular data, display of the two-dimensional spectra, extraction of 1D slices at different wavelengths, and output in various graphic formats. PMID:24984078

  11. Fluorescence and reflectance spectra of freshly excised cervical tissue

    NASA Astrophysics Data System (ADS)

    Zelenchuk, Alex R.; Oliva, Esther; Kaufman, Howard; Schomacker, Kevin T.; Bandarchi-Chamkhaleh, Bizhan; Pitts, Jonathan D.

    2002-05-01

    Fluorescence emission and diffuse reflectance spectra of freshly excised cervical tissue were studied with two specially designed contact probes. The objective of the study was to reach a better understanding of the relationship between spectroscopic measurements and cervical tissue morphology. Tissue samples from loop electro-surgical excision and hysterectomy specimens were measured within 20 to 90 minutes of excision. Emission spectra with 337 nm excitation, and reflectance spectra were collected at wavelengths between 370 and 720 nm from different tissue sites. Hematoxylin-eosin stained slides of the measured zones were obtained and compared to the spectra. In one experiment, a contact probe with a central illumination fiber and two concentric rings of detection fibers (radii 0.1 and 1 mm), was placed in contact with the epithelium and used to measure spectra from ectocervix and endocervix. The influence of 5% acetic acid on fluorescence and reflectance spectra was also investigated. In another experiment, a single 100-micron fiber probe was placed perpendicular to a cut edge of tissue and scanned to measure spectra in depth. Depth scans were made over various areas of the cervix

  12. 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

  13. 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.

  14. 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.

  15. The photophysics of phenylenevinylene oligomers and self-absorption of their fluorescence in polymer films.

    PubMed

    Winch, Nicola M; Smith, Gerald J; Breukers, Robert D; Bhuiyan, Delower H; Kay, Andrew J; Smith, Trevor A; Ghiggino, Kenneth P; Raymond, Sebastiampillai G

    The fluorescence spectra, quantum yields and lifetimes of a series of alkoxy-substituted phenylenevinylene molecules, which serve as short chain oligomer models for poly(p-phenylenevinylene), have been determined in fluid solvents and in a high viscosity polymer matrix. The effects of solvent polarity and a high viscosity molecular environment on the fluorescence yields and spectral shapes have been established. Alkoxy group substitution on the phenyl ring moieties of the molecules has an important effect on the vibronic structures and profiles of the absorption spectra. This was interpreted in terms of hot-band, ground to excited singlet state transitions from energetically closely-spaced torsional vibrational levels of the vinylene double bond in the ground state. The shapes of the absorption bands affect the overlaps of the absorption and fluorescence spectra. This has been quantified as the probability of fluorescence reabsorption in solid polymer films as a function of pathlength. This is an important determinant of the efficacies of these compounds for "harvesting" solar energy in luminescent solar concentrator systems. The reabsorption probabilities of these compounds are lower for all pathlengths than those determined in the same polymer film for the fluorophores, perylene and perylene diimide, which have been considered for concentrating spatially diffuse sunlight. PMID:27480331

  16. [The measurement and analysis of visible-absorption spectrum and fluorescence spectrum of lycopene].

    PubMed

    Yang, Xiao-zhan; Li, Ping; Dai, Song-hui; Wu, Da-cheng; Li, Rui-xia; Yang, Jian-hui; Xiao, Hai-bo

    2005-11-01

    Using ICCD spectral detection system, the absorbency of lycopene-carbon bisulfide solution with different concentration was measured, and the result shows that in a specified range the absorption rule of lycopene solution agrees with Lambert-Beer Law. Absorption spectral wavelength shifts were measured respectively when lycopene was dissolved in acetone, normal hexane, petroleum ether, benzene, ethyl acetate, and carbon bisulfide, and comparing to acetone, different red-shift appeared when lycopene was dissolved in benzene, ethyl acetate, and carbon bisulfide when water was added in lycopene-acetone solution, t he absorbency of lycopene dropped, the fine structure of absorption spectrum became indistinct, and a new absorption peak appeared in UV. The reason for these phenomena is that the solvent molecule had different effect on lycopene molecule when lycopene was dissolved in different solvent. Using fluorecence spectrophotometer, fluorescence spectra of lycopene in different concentrations were collected, and the results show that the fluorescence spectra of lycopene were mainly in 500-680 nm. When concentration was lower than 50 microg x mL(-1), the fluorescence intensity linearly increased with increasing concentration, and when concentration was higher than 60 microg x mL(-1), the fluorescence intensity dropped because of the interaction between lycopene molecules. PMID:16499057

  17. Correction of ultraviolet-induced fluorescence spectra for the examination of polychromy.

    PubMed

    Verri, Giovanni; Clementi, Catia; Comelli, Daniela; Cather, Sharon; Piqué, Francesca

    2008-12-01

    Ultraviolet-induced fluorescence spectroscopy is a commonly used technique for the characterization and identification of painting materials, such as organic binders and colorants. Its interpretation is strictly connected to both the experimental setup and an understanding of the physical and chemical interactions among materials in paint layers, which are commonly composed of a fluorescent organic binder and a pigment. When irradiated with ultraviolet radiation, the light emitted by fluorophores present in the organic binder undergoes several types of interactions, in particular scattering and absorption by neighboring pigmented particles and auto-absorption. As a result of scattering and absorption phenomena, the emission spectrum is deformed according to the physical properties of the surrounding pigmented particles. This can lead to shifts of the emission maxima and/or to the formation of apparent new emission bands. The extent of the modifications to the emission spectra, caused by auto-absorption and selective absorption phenomena, may lead to the erroneous characterization or identification of the fluorescent materials. As a consequence, the interpretation of the emission signal can be greatly compromised. A correction based on the Kubelka-Munk theory is proposed to evaluate the extent of the spectral distortion and is assessed on modern replicas of wall paintings of known composition. Although the model cannot be applied to all cases, qualitative distinctions between real and apparent emissions are achieved. PMID:19094387

  18. 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.

  19. 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.

  20. Fluorescence spectra decomposition by asymmetric functions: Laurdan spectrum revisited.

    PubMed

    Bacalum, Mihaela; Zorilă, Bogdan; Radu, Mihai

    2013-09-15

    Due to their asymmetric nature, complex fluorescence spectra of molecules can be analyzed much better by log-normal distributions than by Gaussian ones. So far, the log-normal function has been used for deconvolution of emission spectra of different fluorescent molecules, such as Tryptophan and Prodan, but to our knowledge it is far less used for Laurdan (2-dimethylamino-6-lauroylnaphthalene). In this article, we present the decomposition of Laurdan emission spectra in large unilamellar vesicles using a procedure that relies on the log-normal asymmetric function. The procedure was calibrated using Laurdan spectra in homogeneous solutions of various solvents. Comparing our results with the ones obtained from a Gaussian fit, we show that (i) the position of the elementary peaks (~440 and 490 nm) is preserved in a large range of temperatures that include the main phase transition of lipid bilayer and (ii) the bilayer hydration, as reported by Laurdan, increases approximately 8 times from the gel phase to the liquid crystalline one, a result that fits with other reports, providing a more realistic description. In addition, we propose a new parameter to globally evaluate Laurdan emission spectra with the prospect of acquiring a larger range of values than the classical "generalized polarization". PMID:23747535

  1. Measurement of Fluorescence Spectra from Ambient Aerosol Particles Using Laser-induced Fluorescence Technique

    NASA Astrophysics Data System (ADS)

    Taketani, F.; Kanaya, Y.; Nakamura, T.; Moteki, N.; Takegawa, N.

    2011-12-01

    To obtain the information of composition of organic aerosol particles in atmosphere, we developed an instrument using laser-induced fluorescence (LIF) technique. To measure the fluorescence from a particle, we employed two lasers. Scattering light signal derived from a single particle upon crossing the 635nm-CW laser triggers the 266nm-pulsed laser to excite the particle. Fluorescence from the particle in the wavelength range 300-600nm is spectrally dispersed by a grating spectrometer and then detected by a 32-Ch photo-multiplier tube(PMT). The aerosol stream is surrounded by a coaxial sheath air flow and delivered to the optical chamber at atmospheric pressure. Using PSL particles with known sizes, we made a calibration curve to estimate particle size from scattering light intensity. With the current setup of the instrument we are able to detect both scattering and fluorescence from particles whose diameters are larger than 0.5um. Our system was able to differentiate particles composed of mono-aromatic species (e.g. Tryptophan) from those of Riboflavin, by their different fluorescence wavelengths. Also, measurements of fluorescence spectra of ambient particles were demonstrated in our campus in Yokosuka city, facing Tokyo bay in Japan. We obtained several types of florescence spectra in the 8 hours. Classification of the measured fluorescence spectra will be discussed in the presentation.

  2. Absorption Reconstruction Improves Biodistribution Assessment of Fluorescent Nanoprobes Using Hybrid Fluorescence-mediated Tomography

    PubMed Central

    Gremse, Felix; Theek, Benjamin; Kunjachan, Sijumon; Lederle, Wiltrud; Pardo, Alessa; Barth, Stefan; Lammers, Twan; Naumann, Uwe; Kiessling, Fabian

    2014-01-01

    Aim: Fluorescence-mediated tomography (FMT) holds potential for accelerating diagnostic and theranostic drug development. However, for proper quantitative fluorescence reconstruction, knowledge on optical scattering and absorption, which are highly heterogeneous in different (mouse) tissues, is required. We here describe methods to assess these parameters using co-registered micro Computed Tomography (µCT) data and nonlinear whole-animal absorption reconstruction, and evaluate their importance for assessment of the biodistribution and target site accumulation of fluorophore-labeled drug delivery systems. Methods: Besides phantoms with varying degrees of absorption, mice bearing A431 tumors were imaged 15 min and 48 h after i.v. injection of a fluorophore-labeled polymeric drug carrier (pHPMA-Dy750) using µCT-FMT. The outer shape of mice and a scattering map were derived using automated segmentation of the µCT data. Furthermore, a 3D absorption map was reconstructed from the trans-illumination data. We determined the absorption of five interactively segmented regions (heart, liver, kidney, muscle, tumor). Since blood is the main near-infrared absorber in vivo, the absorption was also estimated from the relative blood volume (rBV), determined by contrast-enhanced µCT. We compared the reconstructed absorption with the rBV-based values and analyzed the effect of using the absorption map on the fluorescence reconstruction. Results: Phantom experiments demonstrated that absorption reconstruction is possible and necessary for quantitative fluorescence reconstruction. In vivo, the reconstructed absorption showed high values in strongly blood-perfused organs such as the heart, liver and kidney. The absorption values correlated strongly with the rBV-based absorption values, confirming the accuracy of the absorption reconstruction. Usage of homogenous absorption instead of the reconstructed absorption map resulted in reduced values in the heart, liver and kidney, by

  3. 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.

  4. 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.

  5. Transition-metal ions in Nd-doped glasses: spectra and effects on Nd fluorescence

    SciTech Connect

    Stokowski, S.E.; Krashkevich, D.

    1985-12-19

    We have measured transition-metal ion (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) spectra and their effects on Nd fluorescence quenching in Nd-doped phosphate and silicate glasses. Our purpose was to determine the maximum allowable impurity content given particular limits on the absorption loss at 1053 nm and the Nd fluorescence quenching rate. To keep the absorption loss <0.1 m/sup -1/ the transition-metal impurity content should be kept below 0.5 ppMw. To keep the increase in the Nd fluorescence decay rate below 1%, the impurity content should be <3 ppMw. We have also found that the Nd quenching rates do not scale as predicted by the Forster-Dexter dipole-dipole energy transfer theory if we assume that the dominant variation with transition metal is the overlap integral of the Nd fluorescence spectrum and the transition-metal absorption. We suggest that phonon-assisted energy transfer to transition metals is effective in quenching Nd. We find that quenching rates increase 1.5 to 4 times as the Nd concentration increases from 0.5 to 10 x 10/sup 20/ cm/sup -3/.

  6. Laser induced fluorescence spectra of fluorophenol cations in a Ne matrix

    USGS Publications Warehouse

    Bondybey, V.E.; English, J.H.; Miller, T.A.; Shiley, R.H.

    1983-01-01

    Laser induced fluorescence and/or absorption spectra of the cations of 2,3,5,6‐tetrafluorophenol, 2,3,5,6‐tetrafluorothiophenol, and 3,5‐difluorophenol have been obtained in a Ne matrix. The spectra of C6HF4OH+ are much better resolved than in the gas phase. The gas phase congestion is likely caused by the near degeneracy of the and electronic states whose separation is now measured at 207 cm−1. The spectrum of C6H3F2OH+ represents a deperturbed example of the Jahn–Teller distorted sym‐C6F3H3+ ion. C6H3F2SH+ shows only a broad featureless absorption.

  7. Interpretation of fluorescence correlation spectra of biopolymer solutions.

    PubMed

    Phillies, George D J

    2016-05-01

    Fluorescence correlation spectroscopy (FCS) is regularly used to study diffusion in non-dilute "crowded" biopolymer solutions, including the interior of living cells. For fluorophores in dilute solution, the relationship between the FCS spectrum G(t) and the diffusion coefficient D is well-established. However, the dilute-solution relationship between G(t) and D has sometimes been used to interpret FCS spectra of fluorophores in non-dilute solutions. Unfortunately, the relationship used to interpret FCS spectra in dilute solutions relies on an assumption that is not always correct in non-dilute solutions. This paper obtains the correct form for interpreting FCS spectra of non-dilute solutions, writing G(t) in terms of the statistical properties of the fluorophore motions. Approaches for applying this form are discussed. PMID:26756528

  8. Experimental research of fluorescence spectra of watercress stressed by lack or excess of watering

    NASA Astrophysics Data System (ADS)

    Bullo, O. A.; Fedotov, Yu. V.; Belov, M. L.; Gorodnichev, V. A.

    2015-11-01

    Experimental laboratory investigations of the laser-induced fluorescence spectra of watercress were conducted. The fluorescence spectra were excited by a YAG:Nd laser emitting at 532 nm. The laboratory setup was described and fluorescence spectra of watercress in stressed states caused by lack and excess of water were presented. It was established that the influence of stress caused by lack and excess of watering is manifested in changes of fluorescence spectra.

  9. 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.

  10. Effect of arsenic on reflectance spectra and chlorophyll fluorescence of aquatic plants.

    PubMed

    Iriel, Analia; Dundas, Gavin; Fernández Cirelli, Alicia; Lagorio, Maria G

    2015-01-01

    Arsenic pollution of groundwater is a serious problem in many regions of Latin America that causes severe risks to human health. As a consequence, non-destructive monitoring methodologies, sensitive to arsenic presence in the environment and able to perform a rapid screening of large polluted areas, are highly sought-after. Both chlorophyll - a fluorescence and reflectance of aquatic plants may be potential indicators to sense toxicity in water media. In this work, the effects of arsenic on the optical and photophysical properties of leaves of different aquatic plants (Vallisneria gigantea, Azolla filiculoides and Lemna minor) were evaluated. Reflectance spectra were recorded for the plant leaves from 300 to 2400 nm. The spectral distribution of the fluorescence was also studied and corrected for light re-absorption processes. Photosynthetic parameters (Fv/Fm and ΦPSII) were additionally calculated from the variable chlorophyll fluorescence recorded with a pulse amplitude modulated fluorometer. Fluorescence and reflectance properties for V. gigantea and A. filiculoides were sensitive to arsenic presence in contrast to the behaviour of L. minor. Observed changes in fluorescence spectra could be interpreted in terms of preferential damage in photosystem II. The quantum efficiency of photosystem II for the first two species was also affected, decreasing upon arsenic treatment. As a result of this research, V. gigantea and A. filiculoides were proposed as bioindicators of arsenic occurrence in aquatic media. PMID:25150973

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Atomic Absorption, Atomic Fluorescence, and Flame Emission Spectrometry.

    ERIC Educational Resources Information Center

    Horlick, Gary

    1984-01-01

    This review is presented in six sections. Sections focus on literature related to: (1) developments in instrumentation, measurement techniques, and procedures; (2) performance studies of flames and electrothermal atomizers; (3) applications of atomic absorption spectrometry; (4) analytical comparisons; (5) atomic fluorescence spectrometry; and (6)…

  17. 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

  18. 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.

  19. Time-resolved fluorescence spectra of arterial fluorescent compounds: reconstruction with the Laguerre expansion technique.

    PubMed

    Maarek, J M; Marcu, L; Snyder, W J; Grundfest, W S

    2000-02-01

    The time-resolved fluorescence spectra of the main arterial fluorescent compounds were retrieved using a new algorithm based on the Laguerre expansion of kernels technique. Samples of elastin, collagen and cholesterol were excited with a pulsed nitrogen laser and the emission was measured at 29 discrete wavelengths between 370 and 510 nm. The expansion of the fluorescence impulse response function on the Laguerre basis of functions was optimized to reproduce the observed fluorescence emission. Collagen lifetime (5.3 ns at 390 nm) was substantially larger than that of elastin (2.3 ns) and cholesterol (1.3 ns). Two decay components were identified in the emission decay of the compounds. For collagen, the decay components were markedly wavelength dependent and hydration dependent such that the emission decay became shorter at higher emission wavelengths and with hydration. The decay characteristics of elastin and cholesterol were relatively unchanged with wavelength and with hydration. The observed variations in the time-resolved spectra of elastin, collagen and cholesterol were consistent with the existence of several fluorophores with different emission characteristics. Because the compounds are present in different proportions in healthy and atherosclerotic arterial walls, characteristic differences in their time-resolved emission spectra could be exploited to assess optically the severity of atherosclerotic lesions. PMID:10687392

  20. 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.

  1. A fluorescent benzothiazole probe with efficient two-photon absorption

    NASA Astrophysics Data System (ADS)

    Echevarria, Lorenzo; Moreno, Iván; Camacho, José; Salazar, Mary Carmen; Hernández, Antonio

    2012-11-01

    In this work, we report the two-photon absorption of 2-[4-(dimethylamino)phenyl]-1,3-benzothiazole-6-carbonitrile (DBC) in DMSO solution pumping at 779 nm with a 10 ns pulse laser-Nd:YAG system. The obtained two-photon absorption cross-section in DBC (407 ± 18 GM) is considerably high. Because DBC is a novel compound and have high values of fluorescence quantum yield, this result is expected to have an impact in biomolecules detection, diagnosis and treatment of cancer. Similar structures have previously been reported to show remarkable antitumour effects.

  2. 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.

  3. 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

  4. Molecular iodine fluorescence spectra generated with helium-neon lasers for spectrometer calibration.

    PubMed

    Williamson, J Charles

    2010-12-01

    Gas-phase molecular iodine laser-induced fluorescence (LIF) spectra were recorded out to 815 nm at 1 cm(-1) resolution using green, yellow, and red helium-neon (HeNe) lasers as excitation sources. Nine previously unreported I(2) B←X absorption transitions accessed by these lasers were identified, and specific rovibronic transition assignments were made for two hundred LIF peaks--more than sixty per laser. These I(2) LIF peaks can be used to calibrate the vacuum wavenumber coordinate of spectrometers to better than 0.1 cm(-1) accuracy. In particular, green HeNe excitation of the I(2) R(106) 28-0 transition leads to strong fluorescence well suited for calibration, with a rotational doublet spacing of 15 cm(-1) and a doublet-to-doublet spacing of 190 cm(-1). Calibration by HeNe I(2) LIF may be an especially valuable technique for Raman spectroscopy applications. PMID:21144161

  5. Absorption and Transport of Fluorescent Brighteners by Microorganisms

    PubMed Central

    Darken, Marjorie A.

    1962-01-01

    The absorption of brighteners by living cells and their transport to subsequent growth is described. Brighteners are highly fluorescent, ultraviolet-absorbing compounds which appear to be essentially nontoxic, stable biological markers. They have been effectively absorbed by growing cultures of bacteria, yeasts, actinomycetes, and higher fungi, with active growth centers evidencing the greatest flourescence. Images FIG. 2 FIG. 3 FIG. 4 FIG. 5 FIG. 6 FIG. 7 FIG. 8 FIG. 9 FIG. 10-11 PMID:14025111

  6. Fluorescence spectra of benign and malignant prostate tissues

    NASA Astrophysics Data System (ADS)

    AlSalhi, M. S.; Masilamani, V.; Atif, M.; Farhat, K.; Rabah, D.; Turki, M. R. Al

    2012-09-01

    In this study, fluorescence emission spectrum (FES), Stokes' shift spectrum (SSS), and reflectance spectrum (RS) of benign (N = 12) and malignant prostate tissues (N = 8) were investigated to discriminate the two types of tissues. The FES was done with the excitation at 325 nm only; SSS with Δλ = 70 and Δλ = 0, the latter being equivalent to reflectance spectra. Of the three modes of spectra, SSS with Δλ = 70 nm showed the best discrimination. There were four important bands, one at 280 nm (due to tryptophan); 320 nm (due to elastin & tryptophan); 355 and 385 (due to NADH) and 440 nm (due to flavin). From the relative intensities of these bands, three ratios were evaluated. Similarly another two ratios were obtained from reflectance spectra and one more from FES. Thus, there are 6 ratio parameters which represent the relative concentration of tryptophan, elastin, nicotinamide adenine dinucleotide (NADH), and flavin. A statistical analysis showed that benign and malignant tissues could be classified with accuracy greater than 90%. This report is only for in vitro analysis; but employing optical fiber, this can be extended to in vivo analysis too, so that benign tumor could be distinguished without surgery.

  7. 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.

  8. 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.

  9. Surface extended x-ray absorption fine structure of low-Z absorbates using fluorescence detection

    SciTech Connect

    Stoehr, J.; Kollin, E.B.; Fischer, D.A.; Hastings, J.B.; Zaera, F.; Sette, F.

    1985-05-01

    Comparison of x-ray fluorescence yield (FY) and electron yield surface extended x-ray absorption fine structure spectra above the S K-edge for c(2 x 2) S on Ni(100) reveals an order of magnitude higher sensitivity of the FY technique. Using FY detection, thiophene (C/sub 4/H/sub 4/S) chemisorption on Ni(100) is studied with S coverages down to 0.08 monolayer. The molecule dissociates at temperatures as low as 100K by interaction with fourfold hollow Ni sites. Blocking of these sites by oxygen leaves the molecule intact.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. A Passive Method for Detecting Vegetation Stress from Orbit: Chlorophyll Fluorescence Spectra from Fraunhofer Lines

    NASA Technical Reports Server (NTRS)

    Theisen, Arnold F.

    2000-01-01

    Solar-stimulated chlorophyll fluorescence measured with the Fraunhofer line depth method has correlated well with vegetation stress in previous studies. However, the instruments used in those studies were limited to a single solar absorption line (e.g. 656.3 nm), obviating the red/far-red ratio (R/FR) method. Optics and detector technology have reached the level whereby multiple, very narrow Fraunhofer lines are resolvable. Thirteen such lines span the visible spectrum in the red to far-red region where chlorophyll fluorescence occurs. Fluorescence intensities at the 13 Fraunhofer line wavelengths were used to model emission spectra. The source data were collected for summer and fall bean crops (Phaseolus vulgaris L.) subjected to various levels of nitrogen fertilization. The intensities were adjusted to account for Fraunhofer line depth and atmospheric transmittance. Multiple R/FR fluorescence ratios, calculated from the modeled fluorescence spectra, correlated strongly with leaf chlorophyll concentration and well with applied nitrogen. The ratio yielding the best correlation with chlorophyll utilized red fluorescence at the 694.5 nm Fraunhofer line and farred fluorescence at the 755.6 nm Fraunhofer line. Twenty R/FR ratios, each evaluated for the maximum differential between low and high (optimal) nitrogen treatments, ranked higher in some cases and lower in others, possibly related to the time of year the crops were grown and the stage of growth of the crops. Ratios with 728.9 nm and 738.9 nm in the denominator consistently ranked in the lowest and next lowest quartile, respectively. Ratios of the 656.3 nm Fraunhofer line and the 755.6 nm line consistently ranked highest for the summer crop. Ratios with 755.6 nm in the denominator ranked in the upper quartile for 10 out of 12 measurement dates. Differences in ratio ranking indicate that physiological conditions may be estimated using selected ratios of Fraunhofer lines within the context of R/FR analysis. A

  16. Corrected fluorescence spectra of fulvic acids isolated from soil and water

    SciTech Connect

    Ewald, M.; Belin, C.; Berger, P.; Weber, J.H.

    1983-08-01

    The fluorescence of humic matter is a ubiquitous phenomenon that occurs for isolated soil and aquatic matter and for natural water samples. This property is used to compare humic substances, but uncorrected emission spectra can be especially misleading for spectra taken on different instruments. This paper details the corrections of emission fluorescence spectra of well-characterized fulvic acids isolated from soil and a fresh-water river. The corrections significantly modify the uncorrected spectra. This effect demonstrates the need for emission spectra corrections before comparing the fluorescence properties of diverse humic matter samples.

  17. Deriving chlorophyll fluorescence emissions of vegetation canopies from high resolution field reflectance spectra

    NASA Astrophysics Data System (ADS)

    Middleton, Elizabeth M.; Corp, Lawrence A.; Daughtry, Craig S.; Entcheva Campbell, Petya K.; Butcher, L. Maryn

    2005-11-01

    Fluorescence of foliage in the laboratory has proven more rigorous than reflectance for correlation to plant physiology. Especially useful are emissions produced from two stable red and far-red chlorophyll fluorescence (ChlF) peaks centered at 685 nm and 735 nm. Methods have been developed elsewhere to extract steady state solar induced fluorescence (SIF) from apparent reflectance of vegetation canopies/landscapes using the Fraunhofer Line Depth (FLD) principal. Our study utilized these methods in conjunction with field-acquired high spectral resolution canopy reflectance spectra obtained in 2004 and 2005 over corn crops and small tree plots of three deciduous species (red maple, tulip poplar, sweet gum). Leaf level measurements were also made of foliage which included ChlF, photosynthesis, and leaf constituents (photosynthetic pigment, carbon (C), and nitrogen (N) contents). As part of ongoing experiments, measurements were made on N application plots within corn (280, 140, 70, and 0 kg N/ha) and tree (0, 37.5, 75, 112.5, 150 kg N /ha) sites at the USDA/Agriculture Research Service in Beltsville, MD. SIF intensities for ChlF were derived directly from canopy reflectance spectra in specific narrow- band regions associated with atmospheric oxygen absorption features centered at 688 and 760 nm. The red/far-red SIF ratio (SIFratio) derived from these field reflectance spectra successfully discriminated foliar pigment ratios altered by N application rates in both corn crops. This ratio was also positively correlated to the C/N ratio at leaf and canopy levels, for the available corn data (e.g., 2004). No consistent N treatment or species differences in SIF were detected in the tree foliage, but additional 2005 data are forthcoming. This study has relevance to future passive satellite remote sensing approaches to monitoring C dynamics from space.

  18. 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.

  19. Fluorescence Excitation-Emission Matrix Regional Integration to Quantify Spectra for Dissolved Organic Matter

    USGS Publications Warehouse

    Chen, W.; Westerhoff, P.; Leenheer, J.A.; Booksh, K.

    2003-01-01

    Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (??i,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (??T,n = ????i,n) was observed for hydrophobic neutral DOM fractions, followed by lower ??T,n values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

  20. 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.

  1. Absorption and fluorescence of alexandrite and of titanium in sapphire and glass

    NASA Technical Reports Server (NTRS)

    Byvik, C. E.; Hess, R. V.; Buoncristiani, A. M.

    1985-01-01

    The fluorescence and absorption data for titanium in crystalline sapphire and titanium doped into two silicate and one phosphate glass structures are analyzed. It is observed that the Ti-doped silicate glass sample exhibits no absorption related to the Ti(III) ion, the Ti-doped phosphate glass is deep blue, the absorption line width of the glass samples are a factor of two larger than that of sapphire, and the absorption peak for the Ti in the glass shifted about 100 nm to the red from the Ti:sapphire absorption peak. This shift reveals that the Ti(III) ion is sensitive to the crystalline environment and not to the glass environment. The photoluminescence spectra for Ti-doped sapphire and alexandrite are compared. It is detected that the Ti:sapphire exhibits a broader spectrum than that for alexandrite with a peak at 750 nm. The three zero phonon transitions of Ti:Al2O3 at liquid nitrogen temperatures are studied.

  2. Fluorescence and UV/VIS absorption spectroscopy studies on polymer blend films for photovoltaics

    NASA Astrophysics Data System (ADS)

    van Stam, Jan; Lindqvist, Camilla; Hansson, Rickard; Ericsson, Leif; Moons, Ellen

    2015-08-01

    The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C71- butyric acid methyl ester (PC70BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %. We have studied TQ1 films, with and without PC70BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene (o-DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC70BM. Furthermore, if using a bad solvent for PC70BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC70BM. Clear differences were found, comparing the TQ1:PC70BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition. The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  5. 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.

  6. 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.

  7. Chlorophyll Fluorescence Emissions of Vegetation Canopies From High Resolution Field Reflectance Spectra

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; Corp, L. A.; Daughtry, C. S. T.; Campbell, P. K. Entcheva

    2006-01-01

    A two-year experiment was performed on corn (Zea mays L.) crops under nitrogen (N) fertilization regimes to examine the use of hyperspectral canopy reflectance information for estimating chlorophyll fluorescence (ChlF) and vegetation production. Fluorescence of foliage in the laboratory has proven more rigorous than reflectance for correlation to plant physiology. Especially useful are emissions produced from two stable red and far-red chlorophyll ChlF peaks centered at 685V10 nm and 735V5 nm. Methods have been developed elsewhere to extract steady state solar induced fluorescence (SF) from apparent reflectance of vegetation canopies/landscapes using the Fraunhofer Line Depth (FLD) principal. Our study utilized these methods in conjunction with field-acquired high spectral resolution canopy reflectance spectra obtained in 2004 and 2005 over corn crops, as part of an ongoing multi-year experiment at the USDA/Agriculture Research Service in Beltsville, MD. A spectroradiometer (ASD-FR Fieldspec Pro, Analytical Spectral Devices, Inc., Boulder, CO) was used to measure canopy radiances 1 m above plant canopies with a 22deg field of view and a 0deg nadir view zenith angle. Canopy and plant measurements were made at the R3 grain fill reproductive stage on 3-4 replicate N application plots provided seasonal inputs of 280, 140, 70, and 28 kg N/ha. Leaf level measurements were also made which included ChlF, photosynthesis, and leaf constituents (photosynthetic pigment, carbon (C), and N contents). Crop yields were determined at harvest. SIF intensities for ChlF were derived directly from canopy reflectance spectra in specific narrowband regions associated with atmospheric oxygen absorption features centered at 688 and 760 nm. The red/far-red S F ratio derived from these field reflectance spectra successfully discriminated foliar pigment levels (e.g., total chlorophyll, Chl) associated with N application rates in both corn crops. This canopy-level spectral ratio was also

  8. Study on fluorescence spectra of thiamine, riboflavin and pyridoxine

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Xiao, Xue; Zhao, Xuesong; Hu, Lan; Lv, Caofang; Yin, Zhangkun

    2016-01-01

    This paper presents the intrinsic fluorescence characteristics of vitamin B1, B2 and B6 measured with 3D fluorescence Spectrophotometer. Three strong fluorescence areas of vitamin B2 locate at λex/λem=270/525nm, 370/525nm and 450/525nm, one fluorescence areas of vitamin B1 locates at λex/λem=370/460nm, two fluorescence areas of vitamin B6 locate at λex/λem=250/370nm and 325/370nm were found. The influence of pH of solution to the fluorescence profile was also discussed. Using the PARAFAC algorithm, 10 vitamin B1, B2 and B6 mixed solutions were successfully decomposed, and the emission profiles, excitation profiles, central wavelengths and the concentration of the three components were retrieved precisely through about 5 iteration times.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Electron-Vibrational Coupling and Fluorescence Spectra of Tetra-, Penta-, and Hexacoordinated Chlorophylls c1 and c2.

    PubMed

    Etinski, Mihajlo; Petković, Milena; Ristić, Miroslav M; Marian, Christel M

    2015-08-13

    Chlorophylls (Chls) are a group of pigments related to light absorption, excitation energy, and electron transfer in photosynthetic complexes. Given the importance of intramolecular nuclear motion for these electronic processes, many experimental studies were performed in order to relate its coupling to electronic coordinates of these pigments, but a detailed analysis is still lacking for isolated Chls c1 and c2. To gain insight into the intramolecular motion and fluoroscence spectra of these two pigments in tetra-, penta-, and hexacoodinated states, we performed a quantum chemical study based on density functional theory and multimode harmonic approximation with displaced, distorted, and rotated normal modes. In order to benchmark the employed methods, we simulated the high-resolution fluorescence spectra of tetracoodinated Chls a, b, and d and compared them with available experimental spectra obtained with fluorescence line-narrowing techniques. Although the experimental spectra were obtained for ligand coordinated Chls, qualitatively good agreement was found between the simulated and experimental spectra. Almost all resonances were reproduced in the spectroscopically interesting region from 200 to 1700 cm(-1). The significance of mode distortion and rotation for the simulated spectra is discussed. The fluorescence spectra of Chls c1 and c2 consist of a group of peaks in the 200-450 cm(-1) spectral range, a group of weak peaks from 700 to 1000 cm(-1), and a large group of strong peaks from 1100 to 1600 cm(-1). Ligand effects are also addressed, and a mode is identified as a sensitive probe for the coordination state of Chls c1 and c2. PMID:26189597

  16. 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

  17. Aerosol-fluorescence spectrum analyzer: real-time measurement of emission spectra of airborne biological particles

    NASA Astrophysics Data System (ADS)

    Hill, Steven C.; Pinnick, Ronald G.; Nachman, Paul; Chen, Gang; Chang, Richard K.; Mayo, Michael W.; Fernandez, Gilbert L.

    1995-10-01

    We have assembled an aerosol-fluorescence spectrum analyzer (AFS), which can measure the fluorescence spectra and elastic scattering of airborne particles as they flow through a laser beam. The aerosols traverse a scattering cell where they are illuminated with intense (50 kW/cm 2) light inside the cavity of an argon-ion laser operating at 488 nm. This AFS can obtain fluorescence spectra of individual dye-doped polystyrene microspheres as small as 0.5 mu m in diameter. The spectra obtained from microspheres doped with pink and green-yellow dyes are clearly different. We have also detected the fluorescence spectra of airborne particles (although not single particles) made from various

  18. FLUORESCENCE CHARACTERIZATION OF IHSS HUMIC SUBSTANCES: TOTAL LUMINESCENCE SPECTRA WITH ABSORBANCE CORRECTION. (R822251)

    EPA Science Inventory

    Total luminescence spectroscopy was applied to the fluorescence characterization of humic substances obtained from the International Humic Substances Society (IHSS). Results show that total luminescence spectra, represented as excitation-emission matrices (EEMs), may be used to d...

  19. Dimer formation effect on the red-shift in fluorescent spectra of dye solutions

    NASA Astrophysics Data System (ADS)

    Sukprasong, Saksit; Manjit, Yongyut; Limpichaipanit, Apichart; Ngamjarurojana, Athipong

    2015-07-01

    The red-shift on fluorescent dyes spectra at high concentration was investigated by laser induce fluorescence technique. In this research, the fluorescent dyes (Rhodamine 6G, Rhodamine B, Fluorescein and Bromofluorescein) were used. The sample solutions were prepared with methanol solvent in the concentration range of 10-5 to 10-3 Molar and the temperature of sample solution was controlled at 25 °C by temperature control chamber. Then, the sample solution was illuminated by violet laser (405 nm) excitation source and the fluorescence spectra were recorded by CCD spectrometer. The result showed that the fluorescence spectra of all fluorescent dye solutions were dependent on concentration of fluorescent dyes. The position of fluorescence maximum intensity was shifted to a higher wavelength (red-shift) when the concentration increased because the dimer formation rate increases with increasing concentration, but the shifting of wavelength for each fluorescent dye solutions was different, which suggests the different rate of formation of dimer molecules in each fluorescent dye solutions.

  20. 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...

  1. 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.

  2. 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.

  3. Analysis of laser-induced fluorescence spectra of in vitro plant tissue cultures

    NASA Astrophysics Data System (ADS)

    Muñoz-Muñoz, Ana Celia; Gutiérrez-Pulido, Humberto; Rodríguez-Domínguez, José Manuel; Gutiérrez-Mora, Antonia; Rodríguez-Garay, Benjamín; Cervantes-Martínez, Jesús

    2007-04-01

    We demonstrate the effectiveness of laser-induced fluorescence (LIF) for monitoring the development and stress detection of in vitro tissue cultures in a nondestructive and noninvasive way. The changes in LIF spectra caused by the induction of organogenesis, the increase of the F690/F740 ratio as a result of the stress originated in the organogenic explants due to shoot emergence, and the relationship between fluorescence spectra and shoot development were detected by LIF through closed containers of Saintpaulia ionantha.

  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. Measurements of the Ultraviolet Fluorescence Cross Sections and Spectra of Bacillus Anthracis Simulants

    SciTech Connect

    Stephens, J.R.

    1998-09-01

    Measurements of the ultraviolet autofluorescence spectra and absolute cross sections of the Bacillus anthracis (Ba) simulants Bacillus globigii (Bg), Bacillus megaterium (Bm), Bacillus subtilis (Bs), and Bacillus cereus (Bc) were measured. Fluorescence spectra and cross sections of pine pollen (Pina echinata) were measured for comparison. Both dried vegetative cells and spores separated from the sporulated vegetative material were studied. The spectra were obtained by suspending a small number (<10) of particles in air in our Single Particle Spectroscopy Apparatus (SPSA), illuminating the particles with light from a spectrally filtered arc lamp, and measuring the fluorescence spectra of the particles. The illumination was 280 nm (20 nm FWHM) and the fluorescence spectra was measured between 300 and 450 nm. The fluorescence cross section of vegetative Bg peaks at 320 nm with a maximum cross section of 5 X 10{sup -14} cm{sup 2}/sr-nm-particle while the Bg spore fluorescence peaks at 310 nm with peak fluorescence of 8 X 10{sup -15} cm{sup 2}/sr-nm-particle. Pine pollen particles showed a higher fluorescence peaking at 355 nm with a cross section of 1.7 X 10{sup -13} cm{sup 2}/sr-nm-particle. Integrated cross sections ranged from 3.0 X 10{sup -13} for the Bg spores through 2.25 X 10{sup -12} (cm{sup 2}/sr-particle) for the vegetative cells.

  11. [Application of fluorescence spectra and parallel factor analysis in the classification of edible vegetable oils].

    PubMed

    Wu, Xi-jun; Pan, Zhao; Zhao, Yan-peng; Liu, Hai-long; Zheng, Long-jiang

    2014-08-01

    The fluorescence spectra of 22 samples of 8 kinds of edible vegetable oils (soybean oil, maize oil, olive oil, rice oil, peanut oil, walnut oil, sunflower oil and sesame oil) were measured with FS920 fluorescence spectrometer and the fluorescence matrixs (EEMs) were analyzed with parallel factor (PARAFAC) analysis model. To synthesize the capabilities of material characterization and component identification, fluorescence spectra combined with PARAFAC fulfill the classification of vegetable oils. The map feature (peak position, peak value and peak number) was obtained by analyzing three dimensional spectra and con tour maps in the range of emission wavelength from 260 to 750 nm, and excitation wavelengths from 250 to 550 nm. The fluorescent substances (unsaturated fatty acids, vitamin E and its derivatives, chlorophyll and carotenoid) corresponding to spectrum peaks were determined. The factor-number was selected and the components (vitamin E and its derivatives, linoleic acid and linolenic acid, fatty acid oxidation products, vegetable oil oxidation products) corresponding to each factor were ascertained. The four-factor excitation and emission profiles and projection score plots of PARAFAC model were plotted. Different vegetable oils can be characterized and distinguished with the map features of fluorescence spectra and sample projection plots of PARAFAC model. The results demonstrate the capability of the combination of fluorescence spectra technology and four-factor PARAFAC model for differentiating and characterizing vegetable oils. PMID:25474950

  12. Taking the spectral overlap between excitation and emission spectra of fluorescent materials into account with Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Leyre, Sven; Ryckaert, Jana; Acuna, Paula; Audenaert, Jan; Meuret, Youri; Hofkens, Johan; Durinck, Guy; Deconinck, Geert; Hanselaer, Peter

    2014-05-01

    Monte Carlo ray tracing is an important simulation tool in applications where fluorescence is present, e.g. in bio-medical applications and in the design of luminaires and luminescent solar concentrators. A frequently used ray tracing procedure for fluorescence is the `dual stage' approach. In this approach, first, all sources are traced through the system and the rays absorbed in the fluorescent components are stored. Next, the emission from the fluorescent components is traced. This approach does not allow for subsequent re-absorption and re-emission effects in fluorescent materials with a spectral overlap between excitation and emission spectra. In this work, a `multi stage' ray tracing procedure for the simulation of luminescence is presented. Herein, wavelengths are traced from short to long separately and no distinction is made regarding the origin of emission (either a fluorescent component or a source). The presented approach can be easily implemented in existing commercial ray tracing software thus reducing the programming efforts for the new ray tracing algorithm and taking advantage of the strength of the selected ray tracing package concerning the modelling of complex geometrical systems. Both techniques are compared to investigate the influence of the selected ray tracing approach on the efficiency and colour prediction of a remote phosphor LED module.

  13. Vibration and Fluorescence Spectra of Porphyrin-Cored 2,2-Bis(methylol)-propionic Acid Dendrimers

    PubMed Central

    Minaev, Boris; Lindgren, Mikael

    2009-01-01

    Bis-MPA dendron-coated free-base tetraphenylporphyrin and zinc-tetraphenyl-porphyrin (TPPH2 and TPPZn) were studied in comparison with simple porphyrins (H2P, ZnP) by theoretical simulation of their infrared, Raman and electronic absorption spectra, as well as fluorescense emission. Infrared and fluorescence spectra of the dendrimers were measured and interpreted along with time-resolved measurements of the fluorescence. The 0–1 emission band of the dendron substituted TPPZn was found to experience a “heavy substitution”-effect. The 0–1 vibronic emission signal is associated with a longer decay time (approx. 7 - 8 ns) than the 0-0 emission (approx. 1 - 1.5 ns). The former contributed with more relative emission yield for larger dendron substituents, in agreement with the appearance of steady-state emission spectra showing increased contribution from the 0–1 vibronic fluorescence band at 650 nm. No such substitution effect was observed in the electronic or vibrational spectra of the substituted free-base variant, TPPH2. Vibration spectra of the parent porphyrins (H2P, ZnP, TPPH2 and TPPZn) were calculated by density functional theory (DFT) using the B3LYP/6-31G** approximation and a detailed analysis of the most active vibration modes was made based on both literature and our own experimental data. Based on the results of theoretical calculations the wide vibronic bands in the visible region were assigned. The vibronic structure also gave a qualitative interpretation of bands in the electronic absorption spectra as well as in fluorescence emission depending on the size of dendrimer substitution. From the results of time-dependent DFT calculations it is suggested that the TPPZn-cored dendrimers indicate strong vibronic interaction and increased Jahn-Teller distortion of the prophyrin core for larger dendrimer generations. Specifically, this leads to the entirely different behaviour of the emission spectra upon substitution of the TPPH2 and TPPZn variants

  14. 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.

  15. 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.

  16. 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.

  17. An experimental study of the electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles and their electrosynthesized polymers

    NASA Astrophysics Data System (ADS)

    Diaw, A. K. D.; Gningue-Sall, D.; Yassar, A.; Brochon, J.-C.; Henry, E.; Aaron, J.-J.

    2015-01-01

    Electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles (N-PhPys), including HOPhPy, MeOPhPy, ThPhPy, PhDPy, DPhDPy, PyPhThThPhPy, and their available, electrosynthesized polymers were investigated. Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), and other photophysical parameters of these N-PhPy derivatives and their polymers were measured in DMF, DMSO diluted solutions and/or solid state at room temperature. The electronic absorption spectra of N-PhPy derivatives and their polymers included one to several bands, located in the 270-395 nm region, according to the p-phenyl substituent electron-donating effect and conjugated heteroaromatic system length. The fluorescence excitation spectra were characterized by one broad main peak, with, in most cases, one (or more) poorly resolved shoulder (s), appearing in the 270-405 nm region, and their emission spectra were generally constituted of several bands located in the 330-480 nm region. No significant shift of the absorption, fluorescence excitation and emission spectra wavelengths was found upon going from the monomers to the corresponding polymers. ΦF values were high, varying between 0.11 and 0.63, according to the nature of substituents(s) and to the conjugated system extension. Fluorescence decays were mono-exponential for the monomers and poly-exponential for PyPhThThPhPy and for polymers. τF values were relatively short (0.35-5.17 ns), and markedly decreased with the electron-donor character of the phenyl group p-substituent and the conjugated system extension.

  18. An experimental study of the electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles and their electrosynthesized polymers.

    PubMed

    Diaw, A K D; Gningue-Sall, D; Yassar, A; Brochon, J-C; Henry, E; Aaron, J-J

    2015-01-25

    Electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles (N-PhPys), including HOPhPy, MeOPhPy, ThPhPy, PhDPy, DPhDPy, PyPhThThPhPy, and their available, electrosynthesized polymers were investigated. Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), and other photophysical parameters of these N-PhPy derivatives and their polymers were measured in DMF, DMSO diluted solutions and/or solid state at room temperature. The electronic absorption spectra of N-PhPy derivatives and their polymers included one to several bands, located in the 270-395 nm region, according to the p-phenyl substituent electron-donating effect and conjugated heteroaromatic system length. The fluorescence excitation spectra were characterized by one broad main peak, with, in most cases, one (or more) poorly resolved shoulder (s), appearing in the 270-405 nm region, and their emission spectra were generally constituted of several bands located in the 330-480 nm region. No significant shift of the absorption, fluorescence excitation and emission spectra wavelengths was found upon going from the monomers to the corresponding polymers. ΦF values were high, varying between 0.11 and 0.63, according to the nature of substituents(s) and to the conjugated system extension. Fluorescence decays were mono-exponential for the monomers and poly-exponential for PyPhThThPhPy and for polymers. τF values were relatively short (0.35-5.17 ns), and markedly decreased with the electron-donor character of the phenyl group p-substituent and the conjugated system extension. PMID:25173528

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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).

  7. [Fluorescence spectra study of a new toxic protein from Malania oleifera].

    PubMed

    Yuan, Yan; Xiao, Han; Kang, Hong-Jun; Chen, Rui-Yan; Dai, Xiao-Chang

    2009-03-01

    A new toxic protein named malanin was isolated from seeds of Malania olei fera by hydrophobic chromatography, whose cytotoxic activities against carcinoma cells were very strong. The conformational changes of malanin at various temperatures, pH, organic solvents, surfactant, denaturant and fluorescence quenching solvents were studied by fluorescence spectra. The fluorescence spectra of malanin excited at 280 nm and 295 nm showed a maximum at 340 nm. The emission spectra of malanin showed that Trp residues were located by a great degree in the hydrophobic area. Addition of SDS, CH5N3 x HSCN, acrylamide and KI led to changes in the molecular conformation of malanin, and caused the fluorescence quenching of Trp residues. The red-shifted emission band of malanin after adding CH5 N3 x HSCN showed that Trp residues were exposed in polar solvents. PMID:19455822

  8. [Discrimination of Red Tide algae by fluorescence spectra and principle component analysis].

    PubMed

    Su, Rong-guo; Hu, Xu-peng; Zhang, Chuan-song; Wang, Xiu-lin

    2007-07-01

    Fluorescence discrimination technology for 11 species of the Red Tide algae at genus level was constructed by principle component analysis and non-negative least squares. Rayleigh and Raman scattering peaks of 3D fluorescence spectra were eliminated by Delaunay triangulation method. According to the results of Fisher linear discrimination, the first principle component score and the second component score of 3D fluorescence spectra were chosen as discriminant feature and the feature base was established. The 11 algae species were tested, and more than 85% samples were accurately determinated, especially for Prorocentrum donghaiense, Skeletonema costatum, Gymnodinium sp., which have frequently brought Red tide in the East China Sea. More than 95% samples were right discriminated. The results showed that the genus discriminant feature of 3D fluorescence spectra of Red Tide algae given by principle component analysis could work well. PMID:17891964

  9. 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.

  10. 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

  11. 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.

  12. Variability of spectra of laser-induced fluorescence of colonic mucosa: its significance for fluorescence detection of colonic neoplasia.

    PubMed

    Chwirot, Barbara W; Kowalska, Małgorzata; Płóciennik, Natalia; Piwiński, Mariusz; Michniewicz, Zbigniew; Chwirot, Stanisław

    2003-05-01

    To determine the extent of a natural variability of the spectra of the autofluorescence and its significance for a reproducibility of different approaches typically used in studies on fluorescence detection of colonic lesions. Two independent series of experiments have been conducted during three years in the same laboratory. Macroscopic tissue specimens obtained during operations of patients with colonic cancers were studied in vitro. The tissues were excited using UV lines of c.w. He-Cd laser and pulsed nitrogen laser and the autofluorescence spectra were recorded for areas visually diagnosed as normal or pathologically changed mucosa. Natural variability of the autofluorescence spectra of colonic tissues seems to be most important factor limiting sensitivity and specificity of the diagnostic algorithms. The mean fluorescence spectra obtained for normal mucosa and its neoplastic lesions differ significantly but the differences are difficult to observe because of the high natural variability among the individual spectra. Further studies of biological basis of the colonic autofluorescence are necessary for a progress in the field of fluorescence detection of colonic neoplastic lesions. PMID:15244272

  13. Spectroscopy of α,ω-dithienyl polyenes: evidence for two-photon absorption states from fluorescence studies

    NASA Astrophysics Data System (ADS)

    Natarajan, Lalgudi V.; Kirkpatrick, Sean M.; Sutherland, Richard L.; Sowards, Laura A.; Spangler, Charles W.; Fleitz, Paul A.; Cooper, Thomas M.

    1998-10-01

    The photophysics of a series (alpha) ,(omega) -dithienyl polyenes was studied. Both one photon excited fluorescence and fluorescence originating from two photon absorption states were investigated. There is strong evidence of two photon absorption from fluorescence studies in agreement with our earlier studies involving nonlinear absorption.

  14. Temperature, pressure, and bath gas composition dependence of fluorescence spectra and fluorescence lifetimes of toluene and naphthalene

    NASA Astrophysics Data System (ADS)

    Faust, Stephan; Tea, Gabrielle; Dreier, Thomas; Schulz, Christof

    2013-01-01

    Time-resolved fluorescence spectra of gas-phase toluene and naphthalene were investigated upon picosecond laser excitation at 266 nm as a function of temperature (toluene 296-1,025 K, naphthalene 374-1,123 K), pressure (1-10 bar), and bath gas composition (varying concentrations of N2, O2, and CO2) with a temporal resolution of 50 ps. In the investigated temperature range, the fluorescence spectra of both toluene and naphthalene show a significant red-shift, whereas the fluorescence lifetime decreases with increasing temperature, more pronounced for toluene than for naphthalene. Increasing the total pressure of either N2 or CO2 from atmospheric to 10 bar leads to an increase by about 20 % (naphthalene at 373 K) and a decrease by 60 % (toluene at 575 K) in fluorescence lifetimes, respectively. As expected, at atmospheric pressure collisions with O2 shorten the fluorescence lifetime of both toluene and naphthalene significantly, e.g., by a factor of 30 and 90 when changing O2 partial pressure at 373 K from 0 to 0.21 bar, respectively. The fluorescence model of Koban et al. (Appl Phys B 80: 777, 2005) for the dependence of the toluene quantum yield on temperature and O2 partial pressure at atmospheric pressure describes toluene fluorescence lifetimes well within its range of validity. The model is modified to satisfactorily predict effective toluene fluorescence lifetimes in N2 at pressures up to 10 bar. However, it still fails to predict the dependence at simultaneously elevated temperatures and pressures in air as bath gas. Similarly, an empirical model is presented for predicting (relative) fluorescence quantum yields and lifetimes of naphthalene. Although the fitting models have their shortcomings this publication presents a data set of great importance for practical LIF applications, e.g., in-cylinder mixture formation diagnostics in internal combustion engines.

  15. Laser-excited fluorescence spectra of atomic uranium

    SciTech Connect

    Wang Songyue; Jin Changtai; Shen Mingtao; Wang Xiulan

    1987-05-01

    Using a dc-supply hollow-cathode lamp as a source of uranium vapor and a rhodamine 6G dye laser to excite the vapor optically, it was simple and convenient to detect fluorescence from uranium atoms at 753.393, 763.175, and 763.954 nm. We give a detailed discussion of how we eliminated the intense background emissions, which were principally due to the lamp.

  16. Estimating the biodegradability of treated sewage samples using synchronous fluorescence spectra.

    PubMed

    Lai, Tien M; Shin, Jae-Ki; Hur, Jin

    2011-01-01

    Synchronous fluorescence spectra (SFS) and the first derivative spectra of the influent versus the effluent wastewater samples were compared and the use of fluorescence indices is suggested as a means to estimate the biodegradability of the effluent wastewater. Three distinct peaks were identified from the SFS of the effluent wastewater samples. Protein-like fluorescence (PLF) was reduced, whereas fulvic and/or humic-like fluorescence (HLF) were enhanced, suggesting that the two fluorescence characteristics may represent biodegradable and refractory components, respectively. Five fluorescence indices were selected for the biodegradability estimation based on the spectral features changing from the influent to the effluent. Among the selected indices, the relative distribution of PLF to the total fluorescence area of SFS (Index II) exhibited the highest correlation coefficient with total organic carbon (TOC)-based biodegradability, which was even higher than those obtained with the traditional oxygen demand-based parameters. A multiple regression analysis using Index II and the area ratio of PLF to HLF (Index III) demonstrated the enhancement of the correlations from 0.558 to 0.711 for TOC-based biodegradability. The multiple regression equation finally obtained was 0.148 × Index II - 4.964 × Index III - 0.001 and 0.046 × Index II - 1.128 × Index III + 0.026. The fluorescence indices proposed here are expected to be utilized for successful development of real-time monitoring using a simple fluorescence sensing device for the biodegradability of treated sewage. PMID:22164023

  17. Leaf Level Chlorophyll Fluorescence Emission Spectra: Narrow Band versus Full 650-800 nm Retrievals

    NASA Astrophysics Data System (ADS)

    Middleton, E.; Zhang, Q.; Campbell, P. K.; Huemmrich, K. F.; Corp, L.; Cheng, Y.

    2012-12-01

    Recently, chlorophyll fluorescence (ChlF) retrievals in narrow spectral regions (< 1 nm, between 750-770 nm) of the near infrared (NIR) region of Earth's reflected radiation have been achieved from satellites, including the Japanese GOSAT and the European Space Agency's Sciamachy/Envisat. However, these retrievals sample the total full-spectrum ChlF and are made at non-optimal wavelengths since they are not located at the peak fluorescence emission features. We wish to estimate the total full-spectrum ChlF based on emissions obtained at selected wavelengths. For this, we drew upon leaf emission spectra measured on corn leaves obtained from a USDA experimental cornfield in MD (USA). These emission spectra were determined for the adaxial and abaxial (i.e., top and underside) surfaces of leaves measured throughout the 2008 and 2011 growing seasons (n>400) using a laboratory instrument (Fluorolog-3, Horiba Scientific, USA), recorded in either 1 nm or 5 nm increments with monochromatic excitation wavelengths of either 532 or 420 nm. The total ChlF signal was computed as the area under the continuous spectral emission curves, summing the emission intensities (counts per second) per waveband. The individual narrow (1 or 5 nm) waveband emission intensities were linearly related to full emission values, with variable success across the spectrum. Equations were developed to estimate total ChlF from these individual wavebands. Here, we report the results for the average adaxial/abaxial emissions. Very strong relationships were achieved for the relatively high fluorescence intensities at the red chlorophyll peak, centered at 685 nm (r2= 0.98, RMSE = 5.53 x 107 photons/s) and in the nearby O2-B atmospheric absorption feature centered at 688 nm (r2 = 0.94, RMSE = 4.04 x 107), as well as in the far-red peak centered at 740 nm (r2=0.94, RMSE = 5.98 x107). Very good retrieval success occurred for the O2-A atmospheric absorption feature on the declining NIR shoulder centered at 760

  18. Modeling hyperspectral observations of vegetation fluorescence from photosystem level to top-of-atmosphere radiance spectra

    NASA Astrophysics Data System (ADS)

    Verhoef, W.

    2011-12-01

    In support of the candidate ESA mission FLEX, models have been developed to simulate vegetation chlorophyll fluorescence and its observation on the level of single leaves, the canopy and from space. The Fluspect model is based on the PROSPECT leaf model and includes an additional module which calculates the excitation-fluorescence matrix for both sides of the leaf by means of an efficient doubling algorithm. Fluorescence spectra for white incident light, and of course the spectra of reflectance and transmittance, are computed as well. The FluorSAIL model is a numerical variant of SAIL which calculates top-of-canopy fluorescent radiance in the direction of viewing for given incident radiation spectra from the sun and the sky, obtained from the MODTRAN radiative transfer code. In a recent version called FluorSAIL3, high spectral resolution data (0.1 nm) from MODTRAN5 (beta) are used by the model to simulate observations by the candidate FLEX mission. The model computes the directional canopy reflectance with and without fluorescence for the given incident radiation spectra obtained from MODTRAN and the results have been used to evaluate several algorithms for the retrieval of fluorescence from the apparent reflectance signal. In this contribution emphasis will be on the detection of the fluorescence signal, the dependence of fluorescence observations on leaf chlorophyll content and other PROSPECT parameters, canopy structure, and observational conditions, including the properties of the atmosphere. In addition, some attention is paid to the definition of fluorescence quantum efficiencies at photosystem level, leaf level, and canopy level. This is important for the study of the relation between canopy fluorescence and actual photosynthesis. From the simulations it can be concluded that the interpretation of the fluorescence signal is complex, and probably the comparison of actual observations of spectra of fluorescence and reflectance with spectra simulated by a

  19. Fluorescence spectra of blood plasma treated with ultraviolet irradiation in vivo

    NASA Astrophysics Data System (ADS)

    Zalesskaya, G. A.; Maslova, T. O.

    2010-09-01

    We have studied the fluorescence spectra of blood plasma from patients with acute coronary syndrome, and also the effect of therapeutic doses of in vivo ultraviolet blood irradiation (UBI) on the spectra. We have established that the maxima in the fluorescence spectra of the original plasma samples, obtained from unirradiated blood, are located in the wavelength interval 330-340 nm, characteristic for the fluorescence of tryptophan residues. In extracorporeal UBI ( λ = 254 nm), we observed changes in the shape and also both a blue and a red shift in the maxima of the fluorescence spectra, differing in magnitude for blood plasma samples from different patients in the test group. We show that UBI-initiated changes in the fluorescence spectra of the plasma depend on the original pathological disturbances of metabolite levels, and also on the change in the oxygen-transport function of the blood and the acid-base balance, affecting the oxidative stability of the plasma. We have concluded that UV irradiation, activating buffer systems in the blood, has an effect on the universal and specific interactions of the tryptophan residue with the amino acid residues and water surrounding it.

  20. [Research on the 3D fluorescence spectra differentiation of phytoplankton by coiflet2 wavelet].

    PubMed

    Liu, Bao; Su, Rong-Guo; Song, Zhi-Jie; Zhang, Fang; Wang, Xiu-Lin

    2010-05-01

    In the present paper, the authors utilize the wavelet base function coiflet2 (coif2) to analyze the 3D fluorescence spectra of 37 phytoplankton species belonging to 30 genera of 7 divisions, and these phytoplankton species include common species frequently causing harmful algal blooms and most predominant algal species in the inshore area of China Sea. After the Rayleigh and Raman scattering peaks were removed by the Delaunay triangulation interpolation, the fluorescence spectra of those phytoplankton species were transformed with the coiflet2 wavelet, and the scale vectors and the wavelet vectors were candidate for the feature spectra. Based on the testing results by Bayesian analysis, the 3rd scale vectors were the best feature segments at the division level and picked out as the fluorescence division feature spectra of those phytoplankton species, and the group of the 3rd scale vectors, the 2nd and 3rd wavelet vectors were the best feature segments at the genus level and chosen as the fluorescent genus feature spectra of those phytoplankton species. The reference spectra of those phytoplankton species at the division level and that at the genus level were obtained from these feature spectra by cluster analysis, respectively. The reference spectra base for 37 phytoplankton species was composed of 107 reference spectra at the division level and 155 ones at the genus level. Based on this reference spectra base, a fluorometric discriminating method for phytoplankton populations was established by multiple linear regression resolved by the nonnegative least squares. For 1 776 samples of single phytoplankton species, a correct discriminating rate of 97.0% at genus level and 98.1% at division level can be obtained; The correct discriminating rates are more than 92.7% at the genus level and more than 94.8% at the division level for 384 mixed samples from two phytoplankton species. PMID:20672617

  1. Binding phenomena and fluorescence quenching. II: Photophysics of aromatic residues and dependence of fluorescence spectra on protein conformation

    NASA Astrophysics Data System (ADS)

    Callis, Patrik R.

    2014-12-01

    The three amino acids with aromatic ring side chains-phenylalanine (Phe), tyrosine (Tyr), and especially tryptophan (Trp) have played a long and productive role in helping unlock the secrets of protein behavior by optical spectroscopy (absorption, fluorescence, circular dichroism, etc.) In principle, an appropriately placed Trp will undergo fluorescence wavelength and/or intensity changes upon whatever functional process a protein performs. Although perceived to be enigmatic and not well understood, Trp is arguably now better understood than many of the extrinsic probes currently in use. Basic principles of intrinsic tryptophan fluorescence quenching and wavelength shifts in proteins are presented, with strong emphasis on the importance of electrostatics. The condensed description of findings from recent experiments and simulations of tryptophan fluorescence and intrinsic quenching in proteins is designed to help authors in planning and interpreting experimental results of ligand binding studies.

  2. 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.

  3. Evaluation of potential emission spectra for the reliable classification of fluorescently coded materials

    NASA Astrophysics Data System (ADS)

    Brunner, Siegfried; Kargel, Christian

    2011-06-01

    The conservation and efficient use of natural and especially strategic resources like oil and water have become global issues, which increasingly initiate environmental and political activities for comprehensive recycling programs. To effectively reutilize oil-based materials necessary in many industrial fields (e.g. chemical and pharmaceutical industry, automotive, packaging), appropriate methods for a fast and highly reliable automated material identification are required. One non-contacting, color- and shape-independent new technique that eliminates the shortcomings of existing methods is to label materials like plastics with certain combinations of fluorescent markers ("optical codes", "optical fingerprints") incorporated during manufacture. Since time-resolved measurements are complex (and expensive), fluorescent markers must be designed that possess unique spectral signatures. The number of identifiable materials increases with the number of fluorescent markers that can be reliably distinguished within the limited wavelength band available. In this article we shall investigate the reliable detection and classification of fluorescent markers with specific fluorescence emission spectra. These simulated spectra are modeled based on realistic fluorescence spectra acquired from material samples using a modern VNIR spectral imaging system. In order to maximize the number of materials that can be reliably identified, we evaluate the performance of 8 classification algorithms based on different spectral similarity measures. The results help guide the design of appropriate fluorescent markers, optical sensors and the overall measurement system.

  4. 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

  5. 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

  6. 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

  7. 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.

  8. Theoretical Analysis of the Fluorescence Spectra of 7-Azaindole and Its Tautomer

    NASA Astrophysics Data System (ADS)

    Ten, G. N.; Glukhova, O. E.; Slepchenkov, M. M.; Baranov, V. I.

    2016-03-01

    The electronic—vibrational fluorescence spectra of the first, S 0 → 1 L b, and second, S 0 → 1 L a, electronic transitions of 7-azaindole and its tautomer for an isolated state have been calculated. Specific features of structural changes in 7-azaindole and its tautomer upon electronic excitation are determined. Vibrational spectra are assigned for the ground state, and the vibrational structure of fluorescence spectra is interpreted. It is shown that the intensity redistribution between the 6a and 6b oscillations, which is observed in the fluorescence spectrum of the S 0 → 1 L b transition in 7-azaindole, can be explained as a result of intensity borrowing (according to the Herzberg—Teller mechanism) from the 1 L a state.

  9. [Methods of detector response function establishment in X-ray fluorescence spectra analysis].

    PubMed

    Li, Zhe; Tuo, Xian-Guo; Yang, Jian-Bo; Liu, Ming-Zhe; Cheng, Yi; Wang, Lei; Zhou, Jian-Bin

    2012-11-01

    During the measurement and analysis process of X-ray fluorescence spectra, it is very helpful to improve the analyze speed, accuracy and automaticity of X-ray fluorescence spectra analysis by establishing detector response function(DRF), which represents the shape of full energy peak and can provide former basic data for subsequent X-ray analysis technique. For the theory and model of semiconductor DRF in X-ray energy spectrum measurements, methods of three typical detector response function model establishment, key parameters of full energy peak standard deviation and Fano factor calculation, etc. are discussed, and meanwhile, the summarization and contrast of existing studies are shown in this paper. Finally, the suggestion for modeling methods of DRF in X-ray fluorescence spectra measurements is provided. PMID:23387190

  10. Unravelling molecular mechanisms in the fluorescence spectra of doxorubicin in aqueous solution by femtosecond fluorescence spectroscopy.

    PubMed

    Changenet-Barret, Pascale; Gustavsson, Thomas; Markovitsi, Dimitra; Manet, Ilse; Monti, Sandra

    2013-02-28

    Doxorubicin (DOX) is a potent anti-tumoral agent widely used for cancer therapy. Despite numerous studies, the fluorescence properties of DOX, usually exploited for the characterization of the interaction with biological media, have until now led to controversial interpretations, mainly due to self-association of the drug in aqueous solution. We present here the first femtosecond study of DOX based on measurements with the fluorescence up-conversion technique in combination with time-correlated single photon counting using the same laser source. We provide evidence that fluorescence signals of DOX stem from monomers and dimers. DOX dimerization induces a dramatic decrease in the fluorescence quantum yield from 3.9 × 10(-2) to 10(-5) associated with the red shift of the fluorescence spectrum by ~25 nm. While the fluorescence lifetime of the monomer is 1 ns, the dimer fluorescence is found to decay with a lifetime of about 2 ps. In contrast to monomers, the fluorescence anisotropy of dimers is found to be negative. These experimental observations are consistent with an ultrafast internal conversion (<200 fs) between two exciton states, possibly followed by a charge separation process. PMID:23340955

  11. One trinucleus dimethine cyanine dye: Experimental and theoretical studies on molecular structure as well as absorption and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Zhang, D. D.; Wang, L. Y.; Su, J. J.; Zhang, X. F.; Lei, Y. B.; Zhai, G. H.; Wen, Z. Y.

    2013-05-01

    A kind of trinucleus dimethine cyanine dye: 1-methyl-2,6-bis[2-(furan-2-yl)vinyl]pyridinium iodide (1) was synthesized and characterized by 1H NMR, 13C NMR, IR, MS, UV-Vis spectroscopy and elemental analysis. The crystals of dye 1, obtained from slow evaporation of solvent acetone, crystallized in the triclinic space group P - 1 with a = 9.6501(16) Å, b = 10.2308(17) Å, c = 10.7341(17) Å, V = 887.2(3) Å3, and Z = 2 (at 298(2) K), and it was stabilized by the hydrogen bonds and intermolecular face-to-face π⋯π aromatic stacking interactions. Crystallographic, IR, 1H NMR and UV-Vis data of dye 1 were compared with the results of density functional theory (DFT) method, and the calculated molecular geometries, vibrational bands, 1H NMR chemical shifts and UV-Vis maximum absorption were consistent with the experimental results. The fluorescence spectra were predicted in four different solvents with CIS/PCM methods. Compared with experimental values, the absolute deviations of emission maxima were -17.4 nm in chloroform, 6.3 nm in DMSO, 4.9 nm in methanol, and 6.8 nm in water, respectively. And the experimental fluorescence spectra were nicely reproduced by the simulated fluorescence spectra for each solvent.

  12. Analysis of laser-induced fluorescence spectra of in vitro plant tissue cultures.

    PubMed

    Muñoz-Muñoz, Ana Celia; Gutiérrez-Pulido, Humberto; Rodríguez-Domínguez, José Manuel; Gutiérrez-Mora, Antonia; Rodríguez-Garay, Benjamín; Cervantes-Martínez, Jesús

    2007-04-10

    We demonstrate the effectiveness of laser-induced fluorescence (LIF) for monitoring the development and stress detection of in vitro tissue cultures in a nondestructive and noninvasive way. The changes in LIF spectra caused by the induction of organogenesis, the increase of the F690/F740 ratio as a result of the stress originated in the organogenic explants due to shoot emergence, and the relationship between fluorescence spectra and shoot development were detected by LIF through closed containers of Saintpaulia ionantha. PMID:17384731

  13. Principal-components analysis of fluorescence cross-section spectra from pathogenic and simulant bacteria

    NASA Astrophysics Data System (ADS)

    Heaton, Harold I.

    2005-10-01

    Principal-components analysis of a new set of highly resolved (<1 nm) fluorescence cross-section spectra excited at 354.7 nm over the 370 646 nm band has been used to demonstrate the potential ability of UV standoff lidars to discriminate among particular biological warfare agents and simulants over short ranges. The remapped spectra produced by this technique from Bacillus globigii (Bg) and Bacillus anthracis (Ba) spores were sufficiently different to allow them to be cleanly separated, and the Ba spectra obtained from Sterne and Ames strain spores were distinguishable. These patterns persisted as the spectral resolution was subsequently degraded in processing from ˜1 to 34 nm. This is to the author's knowledge the first time that resolved fluorescence spectra from biological warfare agents have been speciated or shown to be distinguishably different from those normally used surrogates by optical spectroscopy.

  14. 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.

  15. Exploring protein solution structure: Second moments of fluorescent spectra report heterogeneity of tryptophan rotamers.

    PubMed

    Gasymov, Oktay K; Abduragimov, Adil R; Glasgow, Ben J

    2015-11-01

    Trp fluorescent spectra appear as a log-normal function but are usually analyzed with λmax, full width at half maximum, and the first moment of incomplete spectra. Log-normal analyses have successfully separated fluorescence contributions from some multi-Trp proteins but deviations were observed in single Trp proteins. The possibility that disparate rotamer environments might account for these deviations was explored by moment spectral analysis of single Trp mutants spanning the sequence of tear lipocalin as a model. The analysis required full width Trp spectra. Composite spectra were constructed using log-normal analysis to derive the inaccessible blue edge, and the experimentally obtained spectra for the remainder. First moments of the composite spectra reflected the site-resolved secondary structure. Second moments were most sensitive for spectral deviations. A novel parameter, derived from the difference of the second moments of composite and simulated log-normal spectra correlated with known multiple heterogeneous rotamer conformations. Buried and restricted side chains showed the most heterogeneity. Analyses applied to other proteins further validated the method. The rotamer heterogeneity values could be rationalized by known conformational properties of Trp residues and the distribution of nearby charged groups according to the internal Stark effect. Spectral heterogeneity fits the rotamer model but does not preclude other contributing factors. Spectral moment analysis of full width Trp emission spectra is accessible to most laboratories. The calculations are informative of protein structure and can be adapted to study dynamic processes. PMID:26119357

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. HST/COS SPECTRA OF DF Tau AND V4046 Sgr: FIRST DETECTION OF MOLECULAR HYDROGEN ABSORPTION AGAINST THE Ly{alpha} EMISSION LINE

    SciTech Connect

    Yang Hao; Linsky, Jeffrey L.; France, Kevin E-mail: jlinsky@jilau1.colorado.edu

    2011-03-20

    We report the first detection of molecular hydrogen (H{sub 2}) absorption in the Ly{alpha} emission line profiles of two classical T Tauri stars (CTTSs), DF Tau and V4046 Sgr, observed by the Hubble Space Telescope/Cosmic Origins Spectrograph. This absorption is the energy source for many of the Lyman-band H{sub 2} fluorescent lines commonly seen in the far-ultraviolet spectra of CTTSs. We find that the absorbed energy in the H{sub 2} pumping transitions from a portion of the Ly{alpha} line significantly differ from the amount of energy in the resulting fluorescent emission. By assuming additional absorption in the H I Ly{alpha} profile along our light of sight, we can correct the H{sub 2} absorption/emission ratios so that they are close to unity. The required H I absorption for DF Tau is at a velocity close to the radial velocity of the star, consistent with H I absorption in the edge-on disk and interstellar medium. For V4046 Sgr, a nearly face-on system, the required absorption is between +100 km s{sup -1} and +290 km s{sup -1}, most likely resulting from H I gas in the accretion columns falling onto the star.

  5. Specific features of Tm3+ doped BiB3O6 glasses fluorescence spectra and their kinetics.

    PubMed

    Majchrowski, A; Jaroszewicz, L; Kuznik, W; Brik, M G; Klosowicz, S; Kityk, I V

    2012-02-15

    Synthesis and spectral fluorescent features of the thulium-doped BiB(3)O(6) glasses are presented. All spectra were recorded using a pulsed (pulse energy ca. 1μJ, pulse duration 10ns) 355nm third harmonic of 10kHz Nd:YAG laser as an excitation source. A laser beam was focused in a backscattering geometry onto about 1mm(2) spot on the surface of a sample. The Andor SR-303i spectrograph equipped with an Andor DH-501 intensified charge coupled device with spectral resolution up to 1nm was used as a spectra recorder. The time-resolution of this system can be as low as 5ns. The decay kinetics was derived from integrated time-resolved spectra. Additionally the absorption and excitation spectra were measured. The main parameters of the Judd-Ofelt analysis were calculated and comparison of the obtained results with corresponding data for other materials was carried out. PMID:22154264

  6. Synthesis, X-ray crystal structure and fluorescent spectra of novel pyrazolo[1,5- a]pyrazin-4(5 H)-one derivatives

    NASA Astrophysics Data System (ADS)

    Zheng, Liang-Wen; Gong, Zhong-Liang; Liu, Wen-Long; Liu, Ying-Rui; Zhao, Bao-Xiang

    2011-10-01

    A series of fluorescent compounds, containing pyrazolo[1,5- a]pyrazin-4(5 H)-one moiety, were designed and synthesized from ethyl 1-(2-oxo-2-phenylethyl)-3-phenyl-1 H-pyrazole-5-carboxylates. The structures of the compounds have been confirmed by IR, 1H NMR, HRMS and X-ray crystal diffraction. The optical properties of the compounds were investigated by UV-vis absorption and fluorescence spectroscopy. The effect of pH on the UV-vis absorption of compound 2a in methanol-H 2O solutions was studied and interpreted by theory calculation. The p Ka value of compound 2a was determined by the absorption spectra.

  7. Filter-fluorescer measurement of low-voltage simulator x-ray energy spectra

    SciTech Connect

    Baldwin, G.T.; Craven, R.E.

    1986-01-01

    X-ray energy spectra of the Maxwell Laboratories MBS and Physics International Pulserad 737 were measured using an eight-channel filter-fluorescer array. The PHOSCAT computer code was used to calculate channel response functions, and the UFO code to unfold spectrum.

  8. Two-Photon-Coincidence Fluorescence Spectra of Cavity Multipolaritons: Novel Signatures of Multiexciton Generation

    PubMed Central

    Roslyak, Oleksiy; Gumbs, Godfrey; Mukamel, Shaul

    2013-01-01

    In a simulation study, we show that correlated two-dimensional frequency-resolved fluorescence spectra of a quantum dot in a microcavity provide a sensitive probe for the distribution of multiexcitons. Polariton couplings lead to a fine structure of Rabi multiplets that allow us to resolve otherwise overlapping features of the different multiexcitons. These may be used to probe multiexciton generation. PMID:20882965

  9. Evidence for excitation of fluorescence in RPE melanin by multiphoton absorption

    NASA Astrophysics Data System (ADS)

    Glickman, Randolph D.; Rockwell, Benjamin A.; Noojin, Gary D.; Stolarski, David J.; Denton, Michael L.

    2002-06-01

    Previously, we reported that ultrashort, near infrared (NIR) laser pulses caused more DNA breakage in cultured retinal pigment epithelial (RPE) cells than did CW, NIR laser radiation delivering a similar radiant exposure. We hypothesized that this difference was due to multiphoton absorption in an intracellular chromophore such as the RPE melanin. We investigated two-photon excitation of fluorescence in a suspension of isolated bovine RPE melanosomes exposed to a 1-KHz train of approximately 50- fsec laser pulses at 810 nm from a Ti:Sapphire laser, and compared this to the fluorescence excited by CW exposures at 406 nm from a Krypton ion laser. Fluorescence was measured with a PC-based spectrometer. The CW sources excited fluorescence with a peak at 525 nm. The fluorescence intensity depended on the irradiance of the sample, as well as the melanosome concentration. Peak fluorescence was obtained with a suspension of ~2 x 107 melanin granules/ml. The 810-nm, ultrashort pulses also excited fluorescence, but with a broader, lower-amplitude peak. The weaker fluorescence signal excited by the 810-nm ultrashort pulse laser for a given melanosome concentration, compared to 406-nm CW excitation, is possibly due to the smaller two- photon absorption cross-section. These results indicate the involvement of multiphoton absorption in DNA damage.

  10. Spectroscopy in an extremely thin vapor cell: Comparing the cell-length dependence in fluorescence and in absorption techniques

    NASA Astrophysics Data System (ADS)

    Sarkisyan, D.; Varzhapetyan, T.; Sarkisyan, A.; Malakyan, Yu.; Papoyan, A.; Lezama, A.; Bloch, D.; Ducloy, M.

    2004-06-01

    We compare the behavior of absorption and of resonance fluorescence spectra in an extremely thin Rb vapor cell as a function of the ratio of L/λ , with L the cell thickness (L˜150 1800 nm) and λ the wavelength of the Rb D2 line (λ=780 mn) . The Dicke-type coherent narrowing [

    G. Dutier et al., Europhys. Lett. 63, 35 (2003)
    ] is observed only in transmission measurements, in the linear regime, with its typical collapse and revival, which reaches a maximum for L= (2n+1) λ/2 ( n integer). It is shown not to appear in fluorescence, whose behavior-amplitude, and spectral width, is more monotonic with L . Conversely, at high-intensity, the sub-Doppler saturation effects are shown to be the most visible in transmission around L=nλ .

  11. [Theoretical study on fluorescence spectra of four kinds of p-substituted curcumin analogues].

    PubMed

    Jia, Fei-Yun; Su, Yu; Ran, Ming; Zhu, Jiang; Zhang, Bo

    2014-04-01

    Four kinds of p-substituted curcumin analogues were optimized at B3LYP/6-31G (d, p) level. On this basis, the excited states geometry structure was optimized by the CIS method, and finally the fluorescence emission spectra were calculated through the TD-DFT method. The results showed that: the four compounds, a large conjugated system, is preferably coplanar structure. Because of introducing hydroxyl and halogen atom on the benzene ring, the molecular pi-electron conjugation is relatively larger, emission wavelength is relatively longer, and fluorescence spectra show different degrees of red shift. As the electron donating group is hydroxy, the fluorescence phenomenon is more obviously red shifted. PMID:25007617

  12. Quantitative absorption and fluorescence studies of NO between 1060 and 2000 A

    NASA Technical Reports Server (NTRS)

    Guest, J. A.; Lee, L. C.

    1981-01-01

    Synchrotron radiation in the 1060 to 2000 A region was used to measure the average absorption and fluorescence cross sections of NO and to determine approximate photodissociation quantum yields. Several vibrational levels of the D(2) sigma(+), E(2) sigma(+), and B(2) delta states have high fluorescence quantum yields. The C(2) and B(2) states do not fluoresce when the excitation energies are above the first dissociation limit, in accord with previous experiments. In general, the fluorescence yields decrease with increasing photon energy. The quantitative measurements are compared with spectroscopic observations and are found to be reasonably consistent.

  13. Resonance fluorescence spectra from coherently driven quantum dots coupled to slow-light photonic crystal waveguides

    NASA Astrophysics Data System (ADS)

    Roy-Choudhury, Kaushik; Mann, Nishan; Manson, Ross; Hughes, Stephen

    2016-06-01

    Using a polaron master equation approach, we investigate the resonance fluorescence spectra from coherently driven quantum dots (QDs) coupled to an acoustic phonon bath and photonic crystal waveguides with a rich local density of photon states (LDOS). Resonance fluorescence spectra from QDs in semiconductor crystals are known to show strong signatures of electron-phonon interactions, but when coupled to a structured photonic reservoir, the QD emission properties are also determined by the frequency dependence of the LDOS of the photon reservoir. Here, we investigate the simultaneous role of coupled photon and phonon baths on the characteristic Mollow triplet spectra from a strongly driven QD. As an example structured photonic reservoir, we first study a photonic crystal coupled cavity waveguide, and find that photons and phonons have counterinteracting effects near the upper mode edge of the coupled-cavity waveguide, thus establishing the importance of their separate roles in determining the emission spectra. The general theory is developed for arbitrary photonic reservoirs and is further applied to determine the resonance fluorescence spectra from a realistic, disordered W1 photonic crystal waveguide showing important photon-phonon interaction effects that are directly relevant to emerging experiments and theoretical proposals.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. Absorption and Luminescence Studies of Some Highly Fluorescent Derivatives of Vitamin B1; Solvent and pH Effects

    NASA Astrophysics Data System (ADS)

    Marciniak, B.; Koput, J.; Kozubek, H.

    1990-08-01

    The influence of solvent on the UV-visible absorption and luminescence spectra of some highly fluorescent vitamin B1 derivatives, the products of the reaction of N-methylated vitamin B1 with cytidine (I), adenosine (II) and 2-amino-4-methylpyridine (III) is studied. Spectroscopic manifestations of protonation of I and II are also investigated using a semiempirical INDO/S CI method. Singlet and triplet energy levels of the free ion and several protonated species are calculated, and transition energies and oscillator strengths are compared with the experimental spectra. Calculated charge densities on heteroatoms in the ground and excited singlet and triplet states are correlated with changes of the experimental pKa values with excitation. The results for I and II are compared with those for the trimethylated pyrichrominium ion (III) previously studied

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Characterization and measurement results of fluorescence in absorption optical filter glass

    NASA Astrophysics Data System (ADS)

    Reichel, S.; Biertümpfel, R.; Engel, A.

    2015-09-01

    Optical filter glasses (absorption filters) are for example used for spectroscopy. The filter glass absorbs the unwanted light and has a nearly angle independent spectral characteristic. The absorbed light can lead to (self-) fluorescence, i. e. the filter glass itself re-emits fluorescence light at a different wavelength - compared to the incident (excitation) light. This fluorescence light can disturb the measurement signal. In order to obtain an optimized optical design the fluorescence properties of the glasses must be known. By knowing fluorescence properties one can design a system with a good signal-to-noise ratio. We will present our measurement set-up for fluorescence measurements of optical filter glass. This set-up was used to obtain fluorescence measurement results for different optical filter glasses. For the first time we present results on the fluorescence level for different optical filter glasses. In addition the effect of excitation wavelength on the fluorescence level will be studied. Besides other factors, fluorescence depends on impurities of the raw material of the glass melt. Due to small fluctuations of the raw material used for the glass production the fluorescence of the same filter glass type can fluctuate from melt-to-melt. Thus, results from different melts will be shown for the same filter glass type.

  5. Influence of Oil-in-Water Emulsions on Fluorescence Properties as Observed by Excitation-Emission Spectra

    NASA Astrophysics Data System (ADS)

    Baszanowska, E.; Zielinski, O.; Otremba, Z.; Toczek, H.

    2013-10-01

    Oil poses a major threat to marine ecosystems. This work describes a set of studies focused on introducing an efficient method for the identification of oil in the form of oil emulsions through fluorescence spectra analyses. Hence the concept of classification of oil pollution in seawater based on fluorescence spectroscopy using a high sensitive fluorimeter [1] suitable for laboratory and in situ measurements is introduced. We consider that this approach, in the future, will make it possible to collect specific fluorescence information allowing us to build a base of the oil standards. Here we examined excitation-emission fluorescence spectra (EEMs) of water containing oil-in-water emulsion prepared artificially under laboratory conditions. Water polluted with oil-in-water emulsion was studied with the objective to estimate differences in three-dimensional fluorescence spectra. Studies included various types of oils and oil concentrations. Essential differences in fluorescence spectra for various oils are indicated.

  6. Site-selective excitation and polarized absorption and emission spectra of trivalent thulium and erbium in strontium fluorapatite

    SciTech Connect

    Gruber, J.B.; Wright, A.O.; Seltzer, M.D.; Zandi, B.; Merkle, L.D.; Hutchinson, J.A.; Morrison, C.A.; Allik, T.H.; Chai, B.H.

    1997-05-01

    Polarized fluorescence spectra produced by site-selective excitation and conventional polarized absorption spectra were obtained for Tm{sup 3+} and Er{sup 3+} ions individually incorporated into single crystals of strontium fluorapatite, Sr{sub 5}(PO{sub 4}){sub 3}F. Substitution of the trivalent rare earth ion for divalent strontium was achieved by passive charge compensation during Czochralski growth of the fluorapatite crystals. Spectra were obtained between 1780 and 345 nm at temperatures from 4 K to room temperature on crystals having the hexagonal structure [P6{sub 3}/m(C{sub 6h}{sup 2})]. The polarized fluorescence spectra due to transitions from multiplet manifolds of Tm{sup 3+}(4f{sup 12}), including {sup 1}D{sub 2}, {sup 1}G{sub 4}, and {sup 3}H{sub 4} to manifolds {sup 3}H{sub 6} (the ground-state manifold), {sup 3}F{sub 4}, {sup 3}H{sub 5}, {sup 3}H{sub 4}, and {sup 3}F{sub 3} were analyzed for the details of the crystal-field splitting of the manifolds. Fluorescence lifetimes were measured for Tm{sup 3+} transitions from {sup 1}D{sub 2}, {sup 1}G{sub 4}, and {sup 3}H{sub 4} at room temperature and from {sup 1}G{sub 4} at 16 K. Results of the analysis indicate that the majority of Tm{sup 3+} ions occupy sites having C{sub s} symmetry. A point-charge lattice-sum calculation was made in which the crystal-field components, A{sub nm}, were determined assuming that trivalent thulium replaces divalent strontium in the metal site having C{sub s} symmetry. Results support the conclusion that the nearest-neighbor fluoride (F{sup {minus}}) is replaced by divalent oxygen (O{sup 2{minus}}), thus preserving overall charge neutrality and local symmetry. Crystal-field splitting calculations predict energy levels in agreement with experimental data. By varying the crystal-field parameters, B{sub nm}, we obtained a rms difference of 7cm{sup {minus}1} between 43 calculated and experimental Stark levels for Tm{sup 3+}(4f{sup 12}) in Tm:SFAP. (Abstract Truncated)

  7. Magnetic fluorescent lamp having reduced ultraviolet self-absorption

    DOEpatents

    Berman, Samuel M.; Richardson, Robert W.

    1985-01-01

    The radiant emission of a mercury-argon discharge in a fluorescent lamp assembly (10) is enhanced by providing means (30) for establishing a magnetic field with lines of force along the path of electron flow through the bulb (12) of the lamp assembly, to provide Zeeman splitting of the ultraviolet spectral line. Optimum results are obtained when the magnetic field strength causes a Zeeman splitting of approximately 1.7 times the thermal line width.

  8. 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.

  9. Study on fluorescence spectra of chlorothalonil residues and the interaction between chlorothalonil and Chinese herbal medicines.

    PubMed

    Ji, Ren-dong; Zhao, Zhi-min; Chen, Meng-lan; Wang, Le-xin; Zhu, Xing-yue

    2015-02-01

    The fluorescence spectrum was studied for the chlorothalonil (0.2928 mg x mL(-1)) using spectrofluorophotometer. The experiment results showed that the characteristic peaks (352 and 366 nm) are found in the spectrum of chlorothalonil standard solution when the excitation wavelength is 320 nm. And it was found that the shoulder peak gradually disappeared at 366 nm, while the fluorescence peak is stable at 352 nm with the decline of the solution concentration The exponential functional relationship between the concentration of chlorothalonil and fluorescence intensity at 352 nm was obtained, and its correlation coefficient is 0.999. The experimental results are consistent with the theoretical formula about fluorescence intensity and concentration The prediction model functions were also obtained through the liner fitting to the chlorothalonil solution of low concentration, and the correlation coefficient is 0. 995. The limit of detection (LOD) is 0.0188 microg x mL(-1), the limit of quantification (LOQ) is 0.0627 microg x mL(-1), and the linear range is 0.0627-28.45 microg x mL(-1). And fluorescence spectra were studied for the mixed system of astragalus, medlar and chlorothalonil. It was found that the fluorescence intensity of chlorothalonil solution is all declined with the addition of two kinds of Chinese Herbal Medicines, which indicates that there is an interaction between them. The decay rate of fluorescence intensity was obtained which is 88.5% and 99.7%, respectively. Then the model functions were established between fluorescence intensity and the volume of addition, and the correlation coefficient is 0.994 and 0.997, respectively. This study provides the experimental foundation for the detection of chlorothalonil residues using fluorescence spectrum. It is shown that it is possible to detect pesticide residues of chlorothalonil using fluorescence spectra directly, and the relevant parameter value satisfied the requirement of testing standard. Therefore

  10. 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.

  11. 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.

  12. 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

  13. Laser Induced Chlorophyll Fluorescence Spectra of Cajanus Cajan L Plant Growing Under Cadmium Stress

    NASA Astrophysics Data System (ADS)

    Gopal, Ram; Pandey, J. K.

    2010-06-01

    Laser-induced Chlorophyll fluorescence (LICF) spectra of Cajanus cajan L leaves treated with different concentrations of Cd (0.05, 0.5 and 1 mM) are recorded at 10 and 20 days after first treatment of cadmium. LICF spectra are recorded in the region of 650-780 nm using violet diode laser (405 nm). LICF spectra of plant leaves show two maxima near 685 and 730nm. Fluorescence induction kinetics (FIK) curve are recorded at 685 and 730 nm with red diode laser (635 nm) for excitation. The fluorescence intensity ratios (FIR) F685/F730 are calculated from LICF spectra and vitality index (Rfd) are determined from FIK curve. FIR and Rfd value are good stress indicator of plant health. These parameters along with chlorophyll content are used to analyze the effect of Cd on wheat plants. The result indicates that higher concentrations of Cd hazardous for photosynthetic activity and health of Arhar plants. The lower concentration of 0.05 mM shows stimulatory response up to 10 days while after 20 days this concentration also shows inhibitory response. R. Gopal, K. B. Mishra, M. Zeeshan, S. M. Prasad, and M. M. Joshi Curr. Sci., 83, 880, 2002 K. B. Mishra and R. Gopal Int. J. Rem. Sen., 29, 157, 2008 R. Maurya, S. M. Prasad, and R. Gopal J. Photochem. Photobio. C: Photochem. Rev., 9, 29, 2008

  14. Delayed fluorescence spectra of intact leaves photoexcited by sunlight measured with a multichannel Fourier-transform chemiluminescence spectrometer

    NASA Astrophysics Data System (ADS)

    Akita, Saeka; Yano, Ayako; Ishii, Hiroshi; Satoh, Chikahiro; Akai, Nobuyuki; Nakata, Munetaka

    2013-06-01

    Delayed fluorescence spectra of intact leaves of Green pak choi (Brassica rapa var. chinensis) were measured with a multichannel Fourier-transform chemiluminescence spectrometer, which we developed recently. The intact samples, photoexcited by sunlight without artificial light sources, showed delayed fluorescence around 740 nm with a lifetime of ˜6 s. The observed spectra were deconvoluted into two Gaussian bands: the delayed fluorescence from photosystem II and photosystem I complexes. Their relative intensities depended on the chlorophyll concentration, but their wavelengths were unchanged.

  15. Estimation of crude oil grade using time-resolved fluorescence spectra.

    PubMed

    Hegazi, E; Hamdan, A

    2002-04-01

    Time-resolved fluorescence (TRF) spectra of six crude oils from the eastern province of Saudi Arabia were excited using a pulsed laser radiation at 250 nm and measured at specific time gates (TG) within the leading and trailing edges of the laser temporal pulse. The spectra showed the presence of a shoulder near 380 nm that systematically decreased in intensity from high-grade to low-grade crudes, and also from earlier to later TGs. The intensities of these shoulders are shown to be useful in estimating the grades of crude oils, particularly when the TRF spectra are measured at TGs within the leading edge of the laser temporal pulse. Contour diagrams depicting the shapes of the TRF spectra as function of TG (within the leading and trailing edges) are also presented to serve as true fingerprints of the crudes. PMID:18968578

  16. Far wing depolarization of light - Generalized absorption profiles. [in laser fluorescence spectroscopy of Sr vapor

    NASA Technical Reports Server (NTRS)

    Thomann, P.; Burnett, K.; Cooper, J.

    1981-01-01

    An absorption (and/or emission) event which takes place during a strong collision is called a 'correlated event'. It is discussed how correlated events affect the far red wing depolarization of fluorescence. Attention is given to an atomic vapor which is irradiated by linearly polarized light of a frequency on the red side of the resonance line. Two limiting cases are considered, corresponding to excitation in the impact region and in the quasi-static wing. In the quasi-static wing, absorption of a photon followed by fluorescence (rather than Rayleigh scattering), occurs mostly during a collision. Correlated events dominate the scattering process. Expressions derived for the polarization of the fluorescent light are applied to far red wing depolarization. It is found that the polarization of the fluorescent light does not go to zero in the far wing, but depends crucially on the detailed nature of the anisotropy in the long-range part of the interatomic potential.

  17. 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.

  18. 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

  19. 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%.

  20. 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.

  1. 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

  2. Ultraviolet Absorption Spectra, AB Initio Calculations, and Carbonyl Wagging Potential Energy Functions of Cyclobutanone, Cyclopentanone, BICYCLO[3.1.0]HEXAN-3-ONE, and TETRAHYDROFURAN-3-ONE

    NASA Astrophysics Data System (ADS)

    Lee, Soono; Dakkouri, Marwan; Choo, Jaebum; Laane, Jaan

    2000-03-01

    The electronic absorption spectra of cyclobutanone, cyclopentanone, bicyclo[3.1.0]hexan-3-one, and tetrahydrofuran-3-one were recorded and analyzed in the 28,000 - 44,000 cm-1 region. Several dozen absorption bands were assigned for each molecule. These arise from combinations of the ring vibrations and the C=O wagging vibrations. Assigned bands were compared with previously recorded jet-cooled fluorescence excitation spectra. Additional C=O out-of-plane wagging bands were found for cyclopentanone and tetrahydrofuran-3-one, and the potential energy functions for this vibration in these molecules were recalculated. These potential energy functions have barriers to inversion reflecting the fact that the carbonyl group is bent out of the ring plane in the S1(n, π*) excited electronic state.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Investigation of relations between skin cancer lesions' images and their fluorescent spectra

    NASA Astrophysics Data System (ADS)

    Pavlova, P.; Borisova, E.; Avramov, L.; Petkova, El.; Troyanova, P.

    2010-03-01

    This investigation is based on images obtained from healthy tissue and skin cancer lesions and their fluorescent spectra of cutaneous lesions derived after optical stimulation. Our analyses show that the lesions’ spectra of are different of those, obtained from normal tissue and the differences depend on the type of cancer. We use a comparison between these “healthy” and “unhealthy” spectra to define forms of variations and corresponding diseases. However, the value of the emitted light varies not only between the patients, but also depending on the position of the tested area inside of one lesion. These variations could be result from two reasons: different degree of damaging and different thickness of the suspicious lesion area. Regarded to the visible image of the lesion, it could be connected with the chroma of colour of the tested area and the lesion homogeneity that corresponds to particular disease. For our investigation, images and spectra of three non-melanoma cutanous malignant tumors are investigated, namely—basal cell carcinoma, squamous cell carcinoma, and keratoacanthoma. The images were processed obtaining the chroma by elimination of the background—healthy tissue, and applying it as a basic signal for transformation from RGB to Lab colorimetric model. The chroma of the areas of emission is compared with the relative value of fluorescence spectra. Specific spectral features are used to develop hybrid diagnostic algorithm (including image and spectral features) for differentiation of these three kinds of malignant cutaneous pathologies.

  10. Fluorescence rejection in Raman spectra of Syncrude Sweet Blend distillation fractions.

    PubMed

    Michaelian, Kirk H; Yuan, Hongqi; Hall, Robert H; Bulmer, J Tim

    2005-11-01

    Four techniques for the reduction or elimination of fluorescence from Raman spectra of Syncrude process samples were examined in this study. These methods are based on the retrieval of Raman bands from differential, or derivative spectra. Differential data were generated by subtracting similar spectra of a given sample obtained in three ways: (a) shifted detection utilizing an array detector and two successive spectrometer settings; (b) shifted excitation (dispersive Raman) where the two spectra are recorded using neighbouring laser lines and ordinary photon counting; (c) shifted excitation (FT-Raman) in which the laser frequency is changed in software before acquisition of the second spectrum. In addition to these differential techniques, derivative spectra were acquired directly with a dispersive Raman system by modulating the wavelength during scanning. These fluorescence rejection methods were applied to two groups of Syncrude Sweet Blend distillation fractions. For light gas oils (boiling range, 195-343 degrees C) the ratio of monocyclic and bicyclic aromatic species was determined and bands due to aliphatic CH(n) groups were characterized. Heavy gas oils (343-524 degrees C) yielded bands that allowed quantitation of monocyclic, bicyclic and total aromatic groups. Bands due to aliphatics were also identified for the heavy gas oils. These results constitute a significant advance compared to the information obtainable using conventional dispersive and FT-Raman spectroscopy for the analysis of hydrocarbon distillation fractions. PMID:16257762

  11. Effects of ozone and relative humidity on fluorescence spectra of octapeptide bioaerosol particles

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Santarpia, Joshua L.; Ratnesar-Shumate, Shanna; Corson, Elizabeth; Eshbaugh, Jonathan; Hill, Steven C.; Williamson, Chatt C.; Coleman, Mark; Bare, Christopher; Kinahan, Sean

    2014-01-01

    The effects of ozone and relative humidity (RH) at common atmospheric levels on the properties of single octapeptide bioaerosol particles were studied using an improved rotating reaction chamber, an aerosol generator, an ultraviolet aerodynamic particle sizer (UVAPS), an improved single particle fluorescence spectrometer (SPFS), and equipments to generate, monitor and control the ozone and RH. Aerosol particles (mean diameter ~2 μm) were generated from a slurry of octapeptide in phosphate buffered saline, injected into the rotating chamber, and kept airborne for hours. Bioaerosols were sampled from the chamber hourly for the measurements of particle-size distribution, concentration, total fluorescence excited at 355-nm, and single particle fluorescence spectra excited at 266-nm and 351-nm under different controlled RH (20%, 50%, or 80%) and ozone concentration (0 or 150 ppb). The results show that: (1) Particle size, concentration, and the 263-nm-excited fluorescence intensity decrease at different rates under different combinations of the RH and ozone concentrations used. (2) The 263-nm-excited UV fluorescence (280-400 nm) decreased more rapidly than the 263-nm-excited visible fluorescence (400-560 nm), and decreased most rapidly when ozone is present and RH is high. (3) The UV fluorescence peak near 340 nm slightly shifts to the shorter wavelength (blue-shift), consistent with a more rapid oxidation of tryptophan than tyrosine. (4) The 351/355-nm-excited fluorescence (430-580 nm/380-700 nm) increases when ozone is present, especially when the RH is high. (5) The 351/355-nm-excited fluorescence increase that occurs as the tryptophan emission in the UV decreases, and the observation that these changes occur more rapidly at higher RH with the present of ozone, are consistent with the oxidation of tryptophan by ozone and the conversion of the resulting ozonides to N-formyl kynurenine and kynurenine.

  12. Small fluorescence-activating and absorption-shifting tag for tunable protein imaging in vivo

    PubMed Central

    Plamont, Marie-Aude; Billon-Denis, Emmanuelle; Maurin, Sylvie; Gauron, Carole; Pimenta, Frederico M.; Specht, Christian G.; Shi, Jian; Quérard, Jérôme; Pan, Buyan; Rossignol, Julien; Moncoq, Karine; Morellet, Nelly; Volovitch, Michel; Lescop, Ewen; Chen, Yong; Triller, Antoine; Vriz, Sophie; Le Saux, Thomas; Jullien, Ludovic; Gautier, Arnaud

    2016-01-01

    This paper presents Yellow Fluorescence-Activating and absorption-Shifting Tag (Y-FAST), a small monomeric protein tag, half as large as the green fluorescent protein, enabling fluorescent labeling of proteins in a reversible and specific manner through the reversible binding and activation of a cell-permeant and nontoxic fluorogenic ligand (a so-called fluorogen). A unique fluorogen activation mechanism based on two spectroscopic changes, increase of fluorescence quantum yield and absorption red shift, provides high labeling selectivity. Y-FAST was engineered from the 14-kDa photoactive yellow protein by directed evolution using yeast display and fluorescence-activated cell sorting. Y-FAST is as bright as common fluorescent proteins, exhibits good photostability, and allows the efficient labeling of proteins in various organelles and hosts. Upon fluorogen binding, fluorescence appears instantaneously, allowing monitoring of rapid processes in near real time. Y-FAST distinguishes itself from other tagging systems because the fluorogen binding is highly dynamic and fully reversible, which enables rapid labeling and unlabeling of proteins by addition and withdrawal of the fluorogen, opening new exciting prospects for the development of multiplexing imaging protocols based on sequential labeling. PMID:26711992

  13. Small fluorescence-activating and absorption-shifting tag for tunable protein imaging in vivo.

    PubMed

    Plamont, Marie-Aude; Billon-Denis, Emmanuelle; Maurin, Sylvie; Gauron, Carole; Pimenta, Frederico M; Specht, Christian G; Shi, Jian; Quérard, Jérôme; Pan, Buyan; Rossignol, Julien; Moncoq, Karine; Morellet, Nelly; Volovitch, Michel; Lescop, Ewen; Chen, Yong; Triller, Antoine; Vriz, Sophie; Le Saux, Thomas; Jullien, Ludovic; Gautier, Arnaud

    2016-01-19

    This paper presents Yellow Fluorescence-Activating and absorption-Shifting Tag (Y-FAST), a small monomeric protein tag, half as large as the green fluorescent protein, enabling fluorescent labeling of proteins in a reversible and specific manner through the reversible binding and activation of a cell-permeant and nontoxic fluorogenic ligand (a so-called fluorogen). A unique fluorogen activation mechanism based on two spectroscopic changes, increase of fluorescence quantum yield and absorption red shift, provides high labeling selectivity. Y-FAST was engineered from the 14-kDa photoactive yellow protein by directed evolution using yeast display and fluorescence-activated cell sorting. Y-FAST is as bright as common fluorescent proteins, exhibits good photostability, and allows the efficient labeling of proteins in various organelles and hosts. Upon fluorogen binding, fluorescence appears instantaneously, allowing monitoring of rapid processes in near real time. Y-FAST distinguishes itself from other tagging systems because the fluorogen binding is highly dynamic and fully reversible, which enables rapid labeling and unlabeling of proteins by addition and withdrawal of the fluorogen, opening new exciting prospects for the development of multiplexing imaging protocols based on sequential labeling. PMID:26711992

  14. Self-absorption Effects on Alpha-Induced Atmospheric Nitrogen Fluorescence Yield

    SciTech Connect

    Bachelor, Paula P.; Jordan, David V.; Harper, Warren W.; Cannon, Bret D.; Finn, Erin C.

    2009-12-01

    Nitrogen fluorescence induced by alpha, beta and gamma radiation can be used to detect the presence of radioactive contamination in the environment. Successful measurement of fluorescence yield involves a number of factors, including: known fluorescence signal rate during the measurement; the effective alpha spectrum of the radioactive sources used in the measurement; optical attenuation length of the fluorescence signal in air during the measurement; the absolute throughput of the instrumentation; calibration of the instrumentation; and radiation transport modeling of the "effective" array exposure rate given the spectrum of the alpha particles. Field testing of optical instrumentation was conducted to measure the nitrogen fluorescence yield from the alpha radiation generated from americium-241 (241Am) decay. The 241Am test sources were prepared by direct evaporation of ~1 mCi in nitric acid solution, and some solids were visible on the surface of the sources. A laboratory study was conducted with lower activities of 241Am to determine whether the presence of solids on the surface of the sources prepared both by direct evaporation and by electrodeposition onto stainless steel disks produced sufficient self-absorption to cause a decrease in expected fluorescence. Alpha spectroscopy was used to determine the apparent activity of the sources versus the known activity deposited on the surface. Results from the self-absorption laboratory studies were used to correct the activity values in the model and calculate the nitrogen fluorescence generated by the 241Am during the field experiments.

  15. Quantum counter for correcting fluorescence excitation spectra at 320- to 800-nm wavelengths.

    PubMed

    Nothnagel, E A

    1987-05-15

    A procedure for recording corrected fluorescence excitation spectra to wavelengths as long as 800 nm is described. The procedure involves the use of a commercial spectrofluorometer, which is modified by substituting 1,1',3,3,3',3'-hexamethylindotricarbocyanine perchlorate in place of rhodamine B as the quantum counter dye. This modification is applicable to spectrofluorometers supplied by several different manufacturers and can be accomplished by a user having only modest technical skills. A study of the fluorescence excitation spectrum of bacteriochlorophyll a is presented as an illustration of the use of the procedure. The procedure will be valuable in biological and biochemical studies that involve the use of long-wavelength fluorescent probes of either natural or synthetic origin. PMID:3619023

  16. 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.

  17. 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.

  18. New insights on the fluorescent emission spectra of Prodan and Laurdan.

    PubMed

    Vequi-Suplicy, Cíntia C; Coutinho, Kaline; Lamy, M Teresa

    2015-05-01

    Prodan and Laurdan are fluorescent probes largely used in biological systems. They were synthetized to be sensitive to the environment polarity, and their fluorescent emission spectrum shifts around 120 nm, from cyclohexane to water. Although accepted that their emission spectrum is composed by two emission bands, the origin of these two bands is still a matter of discussion. Here we analyze the fluorescent spectra of Prodan and Laurdan in solvents of different polarities, both by decomposing the spectrum into two Gaussian bands and by computing the Decay Associated Spectra (DAS), the latter with time resolved fluorescence. Our data show that the intensity of the lower energy emission band of Prodan and Laurdan (attributed, in the literature, to the decay of a solvent relaxed state) is higher in cyclohexane than in water, showing a decrease as the polarity of the medium increases. Moreover, in all solvents studied here, the balance between the two emission bands is not dependent on the temperature, strongly suggesting two independent excited states. Both bands were found to display a red shift as the medium polarity increases. We propose here a new interpretation for the two emission bands of Prodan and Laurdan in homogeneous solvents: they would be related to the emission of two independent states, and not to a pair of non-relaxed and solvent relaxed states. PMID:25753230

  19. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

  1. 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

  2. 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

  3. Possible use of pattern recognition for the analysis of Mars rover X-ray fluorescence spectra

    NASA Technical Reports Server (NTRS)

    Yin, Lo I; Trombka, Jacob I.; Seltzer, Stephen M.; Johnson, Robert G.; Philpotts, John A.

    1989-01-01

    On the Mars rover sample-return mission, the rover vehicle will collect and select samples from different locations on the Martian surface to be brought back to earth for laboratory studies. It is anticipated that an in situ energy-dispersive X-ray fluorescence (XRF) spectrometer will be on board the rover. On such a mission, sample selection is of higher priority than in situ quantitative chemical anlaysis. With this in mind, a pattern recognition technique is proposed as a simple, direct, and speedy alternative to detailed chemical analysis of the XRF spectra. The validity and efficacy of the pattern recognition technique are demonstrated by the analyses of laboratory XRF spectra obtained from a series of geological samples, in the form both of standardized pressed pellets and as unprepared rocks. It is found that pattern recognition techniques applied to the raw XRF spectra can provide for the same discrimination among samples as a knowledge of their actual chemical composition.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Enhanced squeezing by absorption

    NASA Astrophysics Data System (ADS)

    Grünwald, P.; Vogel, W.

    2016-04-01

    Absorption is usually expected to be detrimental to quantum coherence effects. However, there have been few studies into the situation for complex absorption spectra. We consider the resonance fluorescence of excitons in a semiconductor quantum well. The creation of excitons requires absorption of the incoming pump-laser light. Thus, the absorption spectrum of the medium acts as a spectral filter for the emitted light. Surprisingly, absorption can even improve quantum effects, as is demonstrated for the squeezing of the resonance fluorescence of the quantum-well system. This effect can be explained by an improved phase matching due to absorption.

  12. 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

  13. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, Geon Joon; Sim, Geon Bo; Choi, Eun Ha; Kwon, Young-Wan; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-01

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  14. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    SciTech Connect

    Lee, Geon Joon Sim, Geon Bo; Choi, Eun Ha; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-14

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  15. Determination of the in vivo redox potential using roGFP and fluorescence spectra obtained from one-wavelength excitation

    NASA Astrophysics Data System (ADS)

    Wierer, S.; Elgass, K.; Bieker, S.; Zentgraf, U.; Meixner, A. J.; Schleifenbaum, F.

    2011-02-01

    The analysis of molecular processes in living (plant) cells such as signal transduction, DNA replication, carbon metabolism and senescence has been revolutionized by the use of green fluorescent protein (GFP) and its variants as specific cellular markers. Many cell biological processes are accompanied by changes in the intracellular redox potential. To monitor the redox potential, a redox-sensitive mutant of GFP (roGFP) was created, which shows changes in its optical properties in response to changes in the redox state of its surrounding medium. For a quantitative analysis in living systems, it is essential to know the optical properties of roGFP in vitro. Therefore, we applied spectrally resolved fluorescence spectroscopy on purified roGFP exposed to different redox potentials to determine shifts in both the absorption and the emission spectra of roGFP. Based on these in vitro findings, we introduce a new approach using one-wavelength excitation to use roGFP for the in vivo analysis of cell biological processes. We demonstrate the ability this technique by investigating chloroplast-located Grx1-roGFP2 expressing Arabidopsis thaliana cells as example for dynamically moving intracellular compartments. This is not possible with the two-wavelength excitation technique established so far, which hampers a quantitative analysis of highly mobile samples due to the time delay between the two measurements and the consequential displacement of the investigated area.

  16. 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.

  17. 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.

  18. Picosecond time-resolved absorption and fluorescence dynamics in the artificial bacteriorhodopsin pigment BR6.11.

    PubMed Central

    Brack, T. L.; Delaney, J. K.; Atkinson, G. H.; Albeck, A.; Sheves, M.; Ottolenghi, M.

    1993-01-01

    The picosecond molecular dynamics in an artificial bacteriorhodopsin (BR) pigment containing a structurally modified all-trans retinal chromphore with a six-membered ring bridging the C11=C12-C13 positions (BR6.11) are measured by picosecond transient absorption and picosecond time-resolved fluorescence spectroscopy. Time-dependent intensity and spectral changes in absorption in the 570-650-nm region are monitored for delays as long as 5 ns after the 7-ps, 573-nm excitation of BR6.11. Two intermediates, J6.11 and K6.11/1, both with enhanced absorption to the red (> 600 nm) of the BR6.11 spectrum are observed within approximately 50 ps. The J6.11 intermediate decays with a time constant of 12 +/- 3 ps to form K6.11/1. The K6.11/1 intermediate decays with an approximately 100-ps time constant to form a third intermediate, K6.11/2, which is observed through diminished 650-nm absorption (relative to that of K6.11/1). No other transient absorption changes are found during the remainder of the initial 5-ns period of the BR6.11 photoreaction. Fluorescence in the 650-900-nm region is observed from BR6.11, K6.11/1, and K6.11/2, but no emission assignable to J6.11 is found. The BR6.11 fluroescence spectrum has a approximately 725-nm maximum which is blue-shifted by approximately 15 nm relative to that of native BR-570 and is 4.2 +/- 1.5 times larger in intensity (same sample optical density). No differences in the profile of the fluorescence spectra of BR6.11 and the intermediates K6.11/1 and K6.11/2 are observed. Following ground-state depletion of the BR6.11 population, the time-resolved fluroescence intensity monitored at 725 nm increases with two time constants, 12 +/- 3 and approximately 100 ps, both of which correlate well with changes in the picosecond transient absorption data. The resonance Raman spectrum of ground-state BR6.11, measured with low-energy, 560-nm excitation, is significantly different from the spectrum of native BR-570, thus confirming that the

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasma

    SciTech Connect

    Galante, M. E.; Magee, R. M.; Scime, E. E.

    2014-05-15

    We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm{sup 2}), narrow bandwidth (0.1 cm{sup −1}) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. Here, we describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the DIII-D tokamak pedestal. The measurements are performed in hydrogen and deuterium plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished with a single lens through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and we present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible. Time resolved measurements also allow us to explore the evolution of the neutral hydrogen density and temperature and effects of wall recycling. We find that the atomic neutral density grows rapidly at the initiation of the discharge, reaching the steady-state value within 1 ms. Additionally, we find that neutral hydrogen atoms are born with 0.08 eV temperatures, not 2 eV as is typically assumed.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.-

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. Evaluation of algorithm methods for fluorescence spectra of cancerous and normal human tissues

    NASA Astrophysics Data System (ADS)

    Pu, Yang; Wang, Wubao; Alfano, Robert R.

    2016-03-01

    The paper focus on the various algorithms on to unravel the fluorescence spectra by unmixing methods to identify cancerous and normal human tissues from the measured fluorescence spectroscopy. The biochemical or morphologic changes that cause fluorescence spectra variations would appear earlier than the histological approach; therefore, fluorescence spectroscopy holds a great promise as clinical tool for diagnosing early stage of carcinomas and other deceases for in vivo use. The method can further identify tissue biomarkers by decomposing the spectral contributions of different fluorescent molecules of interest. In this work, we investigate the performance of blind source un-mixing methods (backward model) and spectral fitting approaches (forward model) in decomposing the contributions of key fluorescent molecules from the tissue mixture background when certain selected excitation wavelength is applied. Pairs of adenocarcinoma as well as normal tissues confirmed by pathologist were excited by selective wavelength of 340 nm. The emission spectra of resected fresh tissue were used to evaluate the relative changes of collagen, reduced nicotinamide adenine dinucleotide (NADH), and Flavin by various spectral un-mixing methods. Two categories of algorithms: forward methods and Blind Source Separation [such as Principal Component Analysis (PCA) and Independent Component Analysis (ICA), and Nonnegative Matrix Factorization (NMF)] will be introduced and evaluated. The purpose of the spectral analysis is to discard the redundant information which conceals the difference between these two types of tissues, but keep their diagnostically significance. The facts predicted by different methods were compared to the gold standard of histopathology. The results indicate that these key fluorophores within tissue, e.g. tryptophan, collagen, and NADH, and flavin, show differences of relative contents of fluorophores among different types of human cancer and normal tissues. The

  15. [Study on the deteriorating course of fresh milk by laser-induced fluorescence spectra].

    PubMed

    Liu, J; Yu, C Q; Li, J Z; Yan, J X

    2001-12-01

    Along with the development of living standard, people's demand for food quality and food hygiene also rises. People demand food not only with rich nutrition, inexpensive price, but also with safety. So food hygiene test is paid common attention of society. Milk is a nourishing food and is loved by people. Sour milk goods from milk is also in great demand. But nourishing foods are good for growing many microbes. Fresh milk and sour milk are easy contaminated by microbes and go bad. Laser-induced fluorescence (LIF) technology is an important part of modern optics. It is broadly applied in biomedicine, diagnostics, test of food hygiene, environment protecting, owing to its high sensitivity, high speed, automation, untouched testing. In this paper, we attempted to LIF technology to test milk food quality. We used the third harmonics pulsed Nd:YAG laser (355 nm) as the exciting source, and a multi-track spectrometer as the detector and measured the intensities of apply LIF of fresh milk and sour milk during their deteriorating course. Test system and test method are introduced, fluorescence spectra of deteriorating course are also attached. The test result makes clear that there are close connection between deteriorating course and fluorescence spectra. PMID:12958890

  16. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  17. 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

  18. 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…

  19. Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

    SciTech Connect

    Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse

    2013-12-10

    A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT4+). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Continuous Fluorescence Imaging of Intracellular Calcium by Use of Ion-Selective Nanospheres with Adjustable Spectra.

    PubMed

    Yang, Chenye; Qin, Yu; Jiang, Dechen; Chen, Hong-Yuan

    2016-08-10

    Continuous fluorescence imaging of intracellular ions in various spectral ranges is important for biological studies. In this paper, fluorescent calcium-selective nanospheres, including calix[4]arene-functionalized bodipy (CBDP) or 9-(diethylamino)-5-[(2-octyldecyl)imino]benzo[a]phenoxazine (ETH 5350) as the chromoionophore, were prepared to demonstrate intracellular calcium imaging in visible or near-IR regions, respectively. The fluorescence of the nanospheres was controlled by the chromoionophore, and thus the spectral range for detection was adjustable by choosing the proper chromoionophore. The response time of the nanospheres to calcium was typically 1 s, which allowed accurate measurement of intracellular calcium. These nanospheres were loaded into cells through free endocytosis and exhibited fluorescence for 24 h, and their intensity was correlated with the elevation of intracellular calcium upon stimulation. The successful demonstration of calcium imaging by use of ion-selective nanospheres within two spectral ranges in 24 h supported that these nanospheres could be applied for continuous imaging of intracellular ions with adjustable spectra. PMID:27408988

  8. [Fluorescence spectra and quantum yield of TiO2 nanocrystals synthesized by alcohothermal method].

    PubMed

    Song, Cui-Hong; Li, Yan-Ting; Li, Jing; Wei, Yong-Ju; Hu, Yu-Zhu; Wei, Yu

    2008-01-01

    Fluorescence spectra and fluorescence quantum yield of TiO2 nanocrystals were studied. Using tetra n-butyl titanate as a starting material, a facile alcohothermal technique was used to synthesize TiO2 nanocrystals. As can be seen from the transmittance electron microscopy (TEM) image, TiO2 nanocrystals with a relatively uniform particle size distribution of < 10 nm are present in the transparent sol. The transparent sol presents a strong stable fluorescence emission with a maximum at 450 nm, which is greatly dependent on the size quantization effects, defect energy level and the surface state of TiO2 nanocrystals. The quantum yield (gamma) of TiO2 was determined by the relative comparison procedure, using freshly prepared analytical purity quinine sulfate in 0.05 mol x L(-1) H2SO4 as a relative quantum yield standard. The emission quantum yield of TiO2 nanocrystals prepared in alcoholic media was calculated to be about 0.20 at wavelengths ranging from 330 to 370 nm, which was much higher than the values reported in previous works. So, it is supposed that nano-TiO2 will be applied as a potential quantum dots fluorescence probe in biological analysis. PMID:18422145

  9. Use of Soller slits to remove reference foil fluorescence from transmission spectra

    PubMed Central

    Tse, Justin J.; George, Graham N.; Pickering, Ingrid J.

    2011-01-01

    Measurement of X-ray absorption spectroscopy (XAS) in transmission is the method of choice for strong or concentrated samples. In a typical XAS experiment above 5 keV the sample is placed between the first (I 0) and second (I 1) ion chambers and a standard foil is placed between the second (I 1) and third (I 2) ion chambers for simultaneous calibration of energy during sample analysis. However, some fluorescence from the foil may be registered in I 1, causing anomalies in the transmission signal of the sample, especially when the sample edge jump is relatively small. To remedy this, Soller slits were constructed and placed between the foil and I 1 to minimize back-fluorescence from the foil. A comparison of blank and standard samples, measured with or without Soller slits or under a worst-case scenario, demonstrates the advantages of Soller slits when analyzing weak signal samples via transmission XAS. PMID:21525664

  10. Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

    PubMed

    Peng, Tong; Lu, Xiao-lan; Su, Rong-guo; Zhang, Dong-mei

    2015-09-01

    Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM

  11. Fluorescence characterization of IHSS humic substances: Total luminescence spectra with absorbance correction

    SciTech Connect

    Mobed, J.J.; Hemmingsen, S.L.; Autry, J.L.; Mcgown, L.B.

    1996-10-01

    Total luminescence spectroscopy was applied to the fluorescence characterization of humic substances obtained from the International Humic Substances Society (IHSS). Results show that total luminescence spectra, represented as excitation-emission matrices (EEMs), may be used to discriminate between soil-derived and aquatic-derived IHSS humic substances and between humic and fulvic acids derived from the same source (soil or aquatic). Ionic strength in the range of 0-1 M KCl and humic substance concentration in the range 5-100 mg/L had little effect on the fluorescence spectral characteristics of the humic substances, while pH had significant effects as expected. Absorbance correction was shown to be essential for accurate representation and comparison of the EEMs of the humic substances at high concentrations. 16 refs., 5 figs., 3 tabs.

  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. 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.

  14. A high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure measurement.

    PubMed

    Murata, Naoyoshi; Kobayashi, Makoto; Okada, Yukari; Suzuki, Takuya; Nitani, Hiroaki; Niwa, Yasuhiro; Abe, Hitoshi; Wada, Takahiro; Mukai, Shingo; Uehara, Hiromitsu; Ariga, Hiroko; Takakusagi, Satoru; Asakura, Kiyotaka

    2015-03-01

    We present the design and performance of a high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure (XAFS) spectra. The cell has a large fluorescence XAFS window (116 mm(ϕ)) near the sample in the cell, realizing a large half-cone angle of 56°. We use a small heater (25 × 35 mm(2)) to heat the sample locally to 873 K. We measured a Pt-SnO2 thin layer on a Si substrate at reaction conditions having a high activity. In situ measurement enables the analysis of the difference XAFS spectra between before and during the reaction to reveal the structure change during the operation. PMID:25832248

  15. [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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Dicyanostilbene-derived two-photon fluorescence dyes with large two-photon absorption cross sections

    NASA Astrophysics Data System (ADS)

    Huang, Chibao; Lin, Changhua; Ren, Anxiang; Yang, Nianfa

    2011-12-01

    Four dicyanostilbene-derived two-photon fluorescence (TPF) dyes were synthesized as the model compounds to systematically study the effect of the dicyano and the terminal substituent on the two-photon absorption (TPA). These four compounds ( DSO, DCY, DTO and DPH) exhibit very large two-photon absorption cross sections ( δ). DCY (A- π-A) with the terminal cyano group has especially high fluorescence quantum yield (0.71) and relatively large δ (1480 GM), while DPH (D- π-A) with the substitutedamino group at its terminus possesses the largest δ (2800 GM) and the longest emission wavelength (620 nm). The idealest terminal substituent should not be the alkoxy group but the substitutedamino group. This class of dicyanostilbene dyes possess small molecule size, large δ (830-2800 GM), long-wavelength emission (459-620 nm) and large Stokes shift (80-206 nm), and are ideal chromophores for TPF labels and probes.

  2. Relationship of CDOM fluorescence and absorption on the South West Florida Shelf

    NASA Astrophysics Data System (ADS)

    Conmy, R. N.; Coble, P. G.; Hastings, R. H.

    2005-12-01

    The WFS is a complex subtropical coastal region affected by multiple river systems. In recent years, the southern portion of the shelf has been the focus of much study due to the initiation of persistent harmful algal blooms. During this time, great effort has been put forth in collecting seasonal measurements of CDOM (Colored Dissolved Organic Matter) inherent optical properties via in situ and discrete sampling techniques. This sizeable dataset now allows for establishing robust regional relationships of CDOM fluorescence and absorption. Discussed here will be factors affecting that relationship and how it covaries with chlorophyll and DOC (Dissolve Organic Carbon). This relationship also demonstrates the potential for using in situ CDOM fluorescence measurements from moored locations to provide reliable CDOM absorption values for current bio-optical models.

  3. Protein and acidosis alter calcium-binding and fluorescence spectra of the calcium indicator indo-1.

    PubMed Central

    Baker, A J; Brandes, R; Schreur, J H; Camacho, S A; Weiner, M W

    1994-01-01

    The fluorescent indicator indo-1 is widely used to monitor intracellular calcium concentration. However, quantitation is limited by uncertain effects of the intracellular environment on indicator properties. The goal of this study was to determine the effects of protein and acidosis on the fluorescence spectra and calcium dissociation constant (Kd) of indo-1. With 350 nm excitation light, the ratio of indo-1 fluorescence in the absence versus the presence of saturating Ca2+ at wavelength lambda (S lambda) and Kd increased with [protein]. At pH 7.3, Kd, S400, and S470, which were 210 nM, 0.033, and 1.433 in the absence of protein, increased to 808 nM, 0.161, and 2.641, respectively, by adding proteins from frog muscle and to 638 nM, 0.304, and 3.039, respectively, by adding proteins from rat heart. Effects of protein on indo-1 fluorescence were reduced at higher [indo-1]. Acidosis (pH 6.3) had separate effects, which were additive to those of protein: in the absence of protein, acidosis increased Kd to 640 nM; frog muscle proteins further increased Kd to 1700 nM. Acidosis also changed S lambda slightly. In summary, interaction with protein or protons alters indo-1 calcium-binding and fluorescence. These findings are consistent with several previous studies and suggest that indo-1 calibration constants need to be derived in the presence of appropriate types of protein, ratio of [indo-1]/[protein], and pH. PMID:7819496

  4. 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

  5. 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

  6. Fluorescence upconversion properties of a class of improved pyridinium dyes induced by two-photon absorption

    NASA Astrophysics Data System (ADS)

    Xu, Guibao; Hu, Dawei; Zhao, Xian; Shao, Zongshu; Liu, Huijun; Tian, Yupeng

    2007-06-01

    We report the fluorescence upconversion properties of a class of improved pyridinium toluene- p-sulfonates having donor- π-acceptor (D- π-A) structure under two-photon excitation at 1064 nm. The experimental results show that both the two-photon excited (TPE) fluorescence lifetime and the two-photon pumped (TPP) energy upconversion efficiency were increased with the enhancement of electron-donating capability of the donor in the molecule. It is also indicated that an overlong alkyl group tends to result in a weakened molecular conjugation, leading to a decreased two-photon absorption (TPA) cross section. By choosing the donor, we can obtain a longest fluorescence lifetime of 837 ps, a highest energy upconversion efficiency of ˜6.1%, and a maximum TPA cross-section of 8.74×10 -48 cm 4 s/photon in these dyes.

  7. Estimation of Biological Oxygen Demand and Chemical Oxygen Demand for Combined Sewer Systems Using Synchronous Fluorescence Spectra

    PubMed Central

    Hur, Jin; Lee, Bo-Mi; Lee, Tae-Hwan; Park, Dae-Hee

    2010-01-01

    Real-time monitoring of water quality for sewer system is required for efficient sewer network design because it provides information on the precise loading of pollutant to wastewater treatment facilities and the impact of loading on receiving water. In this study, synchronous fluorescence spectra and its first derivatives were investigated using a number of wastewater samples collected in sewer systems in urban and non-urban areas, and the optimum fluorescence feature was explored for the estimation of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) concentrations of sewer samples. The temporal variations in BOD and COD showed a regular pattern for urban areas whereas they were relatively irregular for non-urban areas. Irrespective of the sewer pipes and the types of the areas, two distinct peaks were identified from the synchronous fluorescence spectra, which correspond to protein-like fluorescence (PLF) and humic-like fluorescence (HLF), respectively. HLF in sewer samples appears to be associated with fluorescent whitening agents. Five fluorescence characteristics were selected from the synchronous spectra and the first-derivatives. Among the selected fluorescence indices, a peak in the PLF region (i.e., Index I) showed the highest correlation coefficient with both BOD and COD. A multiple regression approach based on suspended solid (SS) and Index I used to compensate for the contribution of SS to BOD and COD revealed an improvement in the estimation capability, showing good correlation coefficients of 0.92 and 0.94 for BOD and COD, respectively. PMID:22319257

  8. Estimation of biological oxygen demand and chemical oxygen demand for combined sewer systems using synchronous fluorescence spectra.

    PubMed

    Hur, Jin; Lee, Bo-Mi; Lee, Tae-Hwan; Park, Dae-Hee

    2010-01-01

    Real-time monitoring of water quality for sewer system is required for efficient sewer network design because it provides information on the precise loading of pollutant to wastewater treatment facilities and the impact of loading on receiving water. In this study, synchronous fluorescence spectra and its first derivatives were investigated using a number of wastewater samples collected in sewer systems in urban and non-urban areas, and the optimum fluorescence feature was explored for the estimation of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) concentrations of sewer samples. The temporal variations in BOD and COD showed a regular pattern for urban areas whereas they were relatively irregular for non-urban areas. Irrespective of the sewer pipes and the types of the areas, two distinct peaks were identified from the synchronous fluorescence spectra, which correspond to protein-like fluorescence (PLF) and humic-like fluorescence (HLF), respectively. HLF in sewer samples appears to be associated with fluorescent whitening agents. Five fluorescence characteristics were selected from the synchronous spectra and the first-derivatives. Among the selected fluorescence indices, a peak in the PLF region (i.e., Index I) showed the highest correlation coefficient with both BOD and COD. A multiple regression approach based on suspended solid (SS) and Index I used to compensate for the contribution of SS to BOD and COD revealed an improvement in the estimation capability, showing good correlation coefficients of 0.92 and 0.94 for BOD and COD, respectively. PMID:22319257

  9. Mathematical model to interpret localized reflectance spectra measured in the presence of a strong fluorescence marker

    NASA Astrophysics Data System (ADS)

    Bravo, Jaime J.; Davis, Scott C.; Roberts, David W.; Paulsen, Keith D.; Kanick, Stephen C.

    2016-06-01

    Quantification of multiple fluorescence markers during neurosurgery has the potential to provide complementary contrast mechanisms between normal and malignant tissues, and one potential combination involves fluorescein sodium (FS) and aminolevulinic acid-induced protoporphyrin IX (PpIX). We focus on the interpretation of reflectance spectra containing contributions from elastically scattered (reflected) photons as well as fluorescence emissions from a strong fluorophore (i.e., FS). A model-based approach to extract μa and μs‧ in the presence of FS emission is validated in optical phantoms constructed with Intralipid (1% to 2% lipid) and whole blood (1% to 3% volume fraction), over a wide range of FS concentrations (0 to 1000 μg/ml). The results show that modeling reflectance as a combination of elastically scattered light and attenuation-corrected FS-based emission yielded more accurate tissue parameter estimates when compared with a nonmodified reflectance model, with reduced maximum errors for blood volume (22% versus 90%), microvascular saturation (21% versus 100%), and μs‧ (13% versus 207%). Additionally, quantitative PpIX fluorescence sampled in the same phantom as FS showed significant differences depending on the reflectance model used to estimate optical properties (i.e., maximum error 29% versus 86%). These data represent a first step toward using quantitative optical spectroscopy to guide surgeries through simultaneous assessment of FS and PpIX.

  10. Mathematical model to interpret localized reflectance spectra measured in the presence of a strong fluorescence marker.

    PubMed

    Bravo, Jaime J; Davis, Scott C; Roberts, David W; Paulsen, Keith D; Kanick, Stephen C

    2016-06-01

    Quantification of multiple fluorescence markers during neurosurgery has the potential to provide complementary contrast mechanisms between normal and malignant tissues, and one potential combination involves fluorescein sodium (FS) and aminolevulinic acid-induced protoporphyrin IX (PpIX). We focus on the interpretation of reflectance spectra containing contributions from elastically scattered (reflected) photons as well as fluorescence emissions from a strong fluorophore (i.e., FS). A model-based approach to extract μa and μ′s in the presence of FS emission is validated in optical phantoms constructed with Intralipid (1% to 2% lipid) and whole blood (1% to 3% volume fraction), over a wide range of FS concentrations (0 to 1000  μg/ml 1000  μg/ml ). The results show that modeling reflectance as a combination of elastically scattered light and attenuation-corrected FS-based emission yielded more accurate tissue parameter estimates when compared with a nonmodified reflectance model, with reduced maximum errors for blood volume (22% versus 90%), microvascular saturation (21% versus 100%), and μs′ (13% versus 207%). Additionally, quantitative PpIX fluorescence sampled in the same phantom as FS showed significant differences depending on the reflectance model used to estimate optical properties (i.e., maximum error 29% versus 86%). These data represent a first step toward using quantitative optical spectroscopy to guide surgeries through simultaneous assessment of FS and PpIX. PMID:26836297

  11. Modeling structure and spectra of the kindling fluorescent protein asFP595

    NASA Astrophysics Data System (ADS)

    Collins, Jack R.; Topol, Igor A.; Savitsky, Alexander P.; Nemukhin, Alexander V.

    2011-03-01

    Modern computational approaches based on quantum mechanical methods to characterize structures and optical spectra of biological chromophores in proteins are intensively used to gain knowledge of events occurring upon of their photoexcitation. Primary attention is paid to the species from the family of the green fluorescent protein applied as biomarkers in living cells. We apply quantum chemical approaches for accurate calculations of the structures of the chromophore binding pockets and to estimate spectral bands corresponding to the S0-S1 optical transitions of the intriguing kindling protein asFP595. Its precursor, the chromoprotein asCP from the sea anemony Anemonia sulcata is characterized by distinctive spectral properties: at low light intensities the wild-type protein is weakly fluorescent with the very low quantum yield, however, high intensity irradiation with green light leads to a drastic increase of quantum yield. This phenomenon is now termed "kindling". In simulations, the model system is designed as a molecular cluster constructed on the basis of available crystal structures of the related protein. The equilibrium geometry of the cluster is optimized using density functional theory approximations. The vertical excitation energies corresponding to the S0-S1 transitions are computed by using the semiempirical ZINDO technique. A special attention is paid to evaluate effects of point mutations in the vicinity of the chromophore group. Theoretical data provide important information on the chromophore properties aiming to interpret the results of experimental studies and applications of this fluorescent protein.

  12. Femtosecond Fluorescence Spectra of Tryptophan in Human γ-Crystallin Mutants: Site-Dependent Ultrafast Quenching

    PubMed Central

    Xu, Jianhua; Chen, Jiejin; Toptygin, Dmitri; Tcherkasskaya, Olga; Callis, Patrik; King, Jonathan; Brand, Ludwig; Knutson, Jay R.

    2012-01-01

    The eye lens crystallin proteins are subject to UV irradiation throughout life, and the photochemistry of damage proceeds through the excited state; thus, their tryptophan (Trp) fluorescence lifetimes are physiologically important properties. The time resolved fluorescence spectra of single Trps in human γD- and γS-crystallins have been measured with both an upconversion spectrophotofluorometer on the 300fs to 100ps time scale, and a time correlated single photon counting apparatus on the 100ps to 10ns time scale, respectively. Three Trps in each wild type protein were replaced by phenylalanine, leading to single-Trp mutants: W68-only and W156-only of HγD- and W72-only and W162-only of HγS-crystallin. These proteins exhibit similar ultrafast signatures: positive definite decay associated spectra (DAS) for 50 – 65ps decay constants that indicate dominance of fast, heterogeneous quenching. The quenched population (judged by amplitude) of this DAS differs among mutants. Trps 68, 156 in human γD- and Trp72 in human γS-crystallin are buried, but water can reach amide oxygen and ring HE1 atoms through narrow channels. QM-MM simulations of quenching by electron transfer predict heterogeneous decay times from 50–500 ps that agree with our experimental results. Further analysis of apparent radiative lifetimes allow us to deduce that substantial subpopulations of Trp are fully quenched in even faster (sub-300 fs) processes for several of the mutants. The quenching of Trp fluorescence of human γD- and γS-crystallin may protect them from ambient light induced photo damage. PMID:19919143

  13. Polarized fluorescence and absorption of macroscopically aligned Light Harvesting Complex II.

    PubMed Central

    van Amerongen, H; Kwa, S L; van Bolhuis, B M; van Grondelle, R

    1994-01-01

    Polarized absorption and fluorescence measurements have been performed at 77 K on isotropic and anisotropic preparations of trimeric Light Harvesting Complex II (LHC-II) from spinach. The results enable a decomposition of the absorption spectrum into components parallel and perpendicular to the trimeric plane. For the first time, it is shown quantitatively that the strong absorption band around 676 nm is polarized essentially parallel to the plane of the trimer, i.e., the average angle between the corresponding transition dipole moments and this plane is at most 12 degrees. The different absorption bands for LHC-II should not be considered as corresponding to individual pigments but to collective excitations of different pigments. Nevertheless, the average angle between the Qy transition dipole moments of all chlorophyll a pigments in LHC-II and the trimeric plane could be determined and was found to be 17.5 degrees +/- 2.5 degrees. For the chlorophyll b pigments, this angle is significantly larger (close to 35 degrees). At 77 K, most of the fluorescence stems from a weak band above 676 nm and the corresponding transition dipole moments are oriented further out of plane than the dipole moments corresponding to the 676-nm band. The results are shown to be of crucial significance for understanding the relation between the LHC-II structure and its spectroscopy. PMID:7948696

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Photobleaching of arterial fluorescent compounds: characterization of elastin, collagen and cholesterol time-resolved spectra during prolonged ultraviolet irradiation.

    PubMed

    Marcu, L; Grundfest, W S; Maarek, J M

    1999-06-01

    To study the photobleaching of the main fluorescent compounds of the arterial wall, we repeatedly measured the time-resolved fluorescence of elastin, collagen and cholesterol during 560 s of excitation with nitrogen laser pulses. Three fluence rate levels were used: 0.72, 7.25 and 21.75 microW/mm2. The irradiation-related changes of the fluorescence intensity and of the time-resolved fluorescence decay constants were characterized for the emission at 390, 430 and 470 nm. The fluorescence intensity at 390 nm decreased by 25-35% when the fluence delivered was 4 mJ/mm2, a common value in fluorescence studies of the arterial wall. Cholesterol fluorescence photobleached the most, and elastin fluorescence photobleached the least. Photobleaching was most intense at 390 nm and least intense at 470 nm such that the emission spectra of the three compounds were markedly distorted by photobleaching. The time-resolved decay constants and the fluorescence lifetime were not altered by irradiation when the fluence was below 4 mJ/mm2. The spectral distortions associated with photobleaching complicate the interpretation of arterial wall fluorescence in terms of tissue content in elastin, collagen and cholesterol. Use of the time-dependent features of the emission that are not altered by photobleaching should increase the accuracy of arterial wall analysis by fluorescence spectroscopy. PMID:10378012

  17. Time-Dependent Density Functional Theory Study of Low-Lying Absorption and Fluorescence Band Shapes for Phenylene-Containing Oligoacenes.

    PubMed

    Jun, Ye

    2015-12-24

    Low-lying band shapes of absorption and fluorescence spectra for a member of a newly synthesized family of phenylene-containing oligoacenes (POA 6) reported in J. Am. Chem. Soc. 2012 , 134 , 15351 are studied theoretically with two different approaches with TIPS-anthracene as a comparison. Underlying photophysics and exciton-phonon interactions in both molecules are investigated in details with the aid of the time-dependent density functional theory and multimode Brownian oscillator model. The first two low-lying excited-states of POA 6 were found to exhibit excitation characteristics spanning entire conjugated backbone despite the presence of antiaromatic phenylene section. Absorption and fluorescence spectra calculated from both time-dependent density functional theory and multimode Brownian oscillator model are shown to reach good agreement with experimental ones. The coupling between phonon modes and optical transitions is generally weak as suggested by the multimode Brownian oscillator model. Broader peaks of POA 6 spectra are found to relate to stronger coupling between low frequency phonon modes such as backbone twisting (with frequency <300 cm(-1)) and optical transitions. Furthermore, POA 6 exhibits weaker exciton-phonon coupling for the phonon modes above 1000 cm(-1) compared to TIPS-anthracene owing to extended conjugated backbone. A significant coupling between an in-plane breathing mode localized around the antiaromatic phenylene segment with frequency at 1687 cm(-1) and optical transitions for the first two excited-states of POA 6 is also observed. PMID:26611665

  18. 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

  19. Probing symmetry and symmetry breaking in resonant soft-x-ray fluorescence spectra of molecules

    SciTech Connect

    Glans, P.; Gunnelin, K.; Guo, J.

    1997-04-01

    Conventional non-resonant soft X-ray emission brings about information about electronic structure through its symmetry and polarization selectivity, the character of which is governed by simple dipole rules. For centro-symmetric molecules with the emitting atom at the inversion center these rules lead to selective emission through the required parity change. For the more common classes of molecules which have lower symmetry or for systems with degenerate core orbitals (delocalized over identical sites), it is merely the local symmetry selectivity that provides a probe of the local atomic orbital contribution to the molecular orbital. For instance, in X-ray spectra of first row species the intensities essentially map the p-density at each particular atomic site, and, in a molecular orbital picture, the contribution of the local p-type atomic orbitals in the LCAO description of the molecular orbitals. The situation is different for resonant X-ray fluorescence spectra. Here strict parity and symmetry selectivity gives rise to a strong frequency dependence for all molecules with an element of symmetry. In addition to symmetry selectivity the strong frequency dependence of resonant X-ray emission is caused by the interplay between the shape of a narrow X-ray excitation energy function and the lifetime and vibrational broadenings of the resonantly excited core states. This interplay leads to various observable effects, such as linear dispersion, resonance narrowing and emission line (Stokes) doubling. Also from the point of view of polarization selectivity, the resonantly excited X-ray spectra are much more informative than the corresponding non-resonant spectra. Examples are presented for nitrogen, oxygen, and carbon dioxide molecules.

  20. 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

  1. 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.

  2. Problems affecting performance of the fluorescent treponemal antibody-absorption test for syphilis.

    PubMed Central

    Hunter, E F; Adams, M R; Orrison, L H; Pender, B J; Larsen, S A

    1979-01-01

    Immunofluorescent staining of Treponema pallidum was studied to clarify the effect of three factors on the results of the fluorescent treponemal antibody-absorption test: (i) heat inactivation of sera at 56 degrees C for 30 min before testing, (ii) use of multicircle slides, and (iii) tungsten illumination to visualize and assess unstained treponemes on reactive as well as nonreactive smears. It was found that serum inactivation before testing was not necessary for detection of immunoglobin G antibody, but an immunoglobulin M prozone was detected in unheated serum. On multicircle slides, it was demonstrated that a false-positive reaction could be obtained in 30 s at 37 and 25 degrees C if a smear where a nonreactive serum had been placed was crossed by a strongly reactive serum from another circle. Tungsten illumination proved necessary for correct assessment of unstained treponemes on all fluorescent treponemal antibody-aborption test smears, reactive or nonreactive. The possible role of these factors in incorrect fluorescent treponemal antibody-absorption test results is discussed. PMID:372219

  3. 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

  4. Excitation and propagation of X-ray fluorescence through thin devices with hollowed ordered structures: comparison of experimental and theoretical spectra.

    PubMed

    Mazuritskiy, M I; Dabagov, S B; Marcelli, A; Lerer, A M; Dziedzic-Kocurek, K

    2016-01-01

    The lack of models describing the propagation of X-rays in waveguides and the interference mechanism between incident and reflected radiation waves hamper the understanding and the control of wave propagation phenomena occurring in many real systems. Here, experimental spectra collected at the exit of microchannel plates (MCPs) under the total X-ray reflection condition are presented. The results are discussed in the framework of a theoretical model in which the wave propagation is enhanced by the presence of a transition layer at the surface. The angular distributions of the propagating radiation at the exit of these MCPs with microchannels of ∼3 µm diameter will also be presented and discussed. These spectra show contributions associated with the reflection of the primary monochromatic beam and with the fluorescence radiation originating from the excitation of atoms composing the surface of the microchannel. The soft X-ray fluorescence spectra collected at the exit of microcapillaries were analyzed in the framework of a wave approximation while diffraction contributions observed at the exit of these hollow X-ray waveguides have been calculated using the Fraunhofer diffraction model for waves in the far-field domain. Data collected at the Si L-edge show that in glassy MCPs the fluorescence radiation can be detected only when the energy of the primary monochromatic radiation is above the absorption edge for grazing angles higher than half of the critical angle of the total reflection phenomenon. Experimental data and simulations of the propagating radiation represent a clear experimental confirmation of the channeling phenomenon of the excited fluorescence radiation inside a medium and point out that a high transmission can be obtained in waveguide optics for parameters relevant to X-ray imaging. PMID:26698074

  5. 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.

  6. Effects of densification on fluorescence spectra and glass structure of Eu3+-doped borate glasses

    NASA Astrophysics Data System (ADS)

    Soga, N.; Hirao, K.; Yoshimoto, M.; Yamamoto, H.

    1988-05-01

    Densified glass specimens of 90 B2O3ṡ10 Na2Oṡ1 Eu2O3 were obtained by applying hydrostatic pressure up to 6 GPa at various temperatures from 250 to 900 °C, and their densities and inhomogeneous bandwidths of Eu3+ fluorescence spectra were determined in order to follow a structural change taking place during densification. The results indicate that the role of hydrostatic pressure is first to eliminate the atomic scale voids usually appearing when quenched from high temperatures and then to increase the fluctuation of local fields around Eu3+ probably due to the distortion of glass network accompanied with a wide variation of bond length. The molecular dynamics simulation of the densified state was also carried out to support the above conclusion.

  7. 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.

  8. Do fluorescence and transient absorption probe the same intramolecular charge transfer state of 4-(dimethylamino)benzonitrile?

    SciTech Connect

    Gustavsson, Thomas; Fujiwara, Takashige; Lim, Edward C.

    2009-07-21

    We present here the results of time-resolved absorption and emission experiments for 4-(dimethylamino)benzonitrile in solution, which suggest that the fluorescent intramolecular charge transfer (ICT) state may differ from the twisted ICT (TICT) state observed in transient absorption.

  9. Serial Femtosecond Crystallography and Ultrafast Absorption Spectroscopy of the Photoswitchable Fluorescent Protein IrisFP.

    PubMed

    Colletier, Jacques-Philippe; Sliwa, Michel; Gallat, François-Xavier; Sugahara, Michihiro; Guillon, Virginia; Schirò, Giorgio; Coquelle, Nicolas; Woodhouse, Joyce; Roux, Laure; Gotthard, Guillaume; Royant, Antoine; Uriarte, Lucas Martinez; Ruckebusch, Cyril; Joti, Yasumasa; Byrdin, Martin; Mizohata, Eiichi; Nango, Eriko; Tanaka, Tomoyuki; Tono, Kensuke; Yabashi, Makina; Adam, Virgile; Cammarata, Marco; Schlichting, Ilme; Bourgeois, Dominique; Weik, Martin

    2016-03-01

    Reversibly photoswitchable fluorescent proteins find growing applications in cell biology, yet mechanistic details, in particular on the ultrafast photochemical time scale, remain unknown. We employed time-resolved pump-probe absorption spectroscopy on the reversibly photoswitchable fluorescent protein IrisFP in solution to study photoswitching from the nonfluorescent (off) to the fluorescent (on) state. Evidence is provided for the existence of several intermediate states on the pico- and microsecond time scales that are attributed to chromophore isomerization and proton transfer, respectively. Kinetic modeling favors a sequential mechanism with the existence of two excited state intermediates with lifetimes of 2 and 15 ps, the second of which controls the photoswitching quantum yield. In order to support that IrisFP is suited for time-resolved experiments aiming at a structural characterization of these ps intermediates, we used serial femtosecond crystallography at an X-ray free electron laser and solved the structure of IrisFP in its on state. Sample consumption was minimized by embedding crystals in mineral grease, in which they remain photoswitchable. Our spectroscopic and structural results pave the way for time-resolved serial femtosecond crystallography aiming at characterizing the structure of ultrafast intermediates in reversibly photoswitchable fluorescent proteins. PMID:26866390

  10. 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.

  11. 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.

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. XAS spectroelectrochemistry: reliable measurement of X-ray absorption spectra from redox manipulated solutions at room temperature.

    PubMed

    Best, Stephen P; Levina, Aviva; Glover, Chris; Johannessen, Bernt; Kappen, Peter; Lay, Peter A

    2016-05-01

    The design and operation of a low-volume spectroelectrochemical cell for X-ray absorption spectroscopy (XAS) of solutions at room temperature is described. Fluorescence XAS measurements are obtained from samples contained in the void space of a 50 µL reticulated vitreous carbon (sponge) working electrode. Both rapid electrosynthesis and control of the effects of photoreduction are achieved by control over the flow properties of the solution through the working electrode, where a good balance between the rate of consumption of sample and the minimization of decomposition was obtained by pulsing the flow of the solution by 1-2 µL with duty cycle of ∼3 s while maintaining a small net flow rate (26-100 µL h(-1)). The performance of the cell in terms of control of the redox state of the sample and minimization of the effects of photoreduction was demonstrated by XAS measurements of aqueous solutions of the photosensitive Fe(III) species, [Fe(C2O4)3](3-), together with that of the electrogenerated [Fe(C2O4)3](4-) product. The current response from the cell during the collection of XAS spectra provides an independent measure of the stability of the sample of the measurement. The suitability of the approach for the study of small volumes of mM concentrations of protein samples was demonstrated by the measurement of the oxidized and electrochemically reduced forms of cytochrome c. PMID:27140154

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

    NASA Astrophysics Data System (ADS)

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

    2002-08-01

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

  19. Picosecond kinetic absorption and fluorescence studies of bovine rhodopsin with a fixed 11-ene.

    PubMed Central

    Buchert, J; Stefancic, V; Doukas, A G; Alfano, R R; Callender, R H; Pande, J; Akita, H; Balogh-Nair, V; Nakanishi, K

    1983-01-01

    A synthetic retinal having a fixed 11-cis geometry has been used to prepare a nonbleachable analogue of bovine rhodopsin. Marked differences in the picosecond absorption and fluorescence behavior of this analogue at room temperature, compared with that of natural rhodopsin, were observed. This not only indicates that the 11-cis to trans isomerization of the retinal moiety is the crucial primary event in the photolysis of rhodopsin, but also it establishes that this isomerization must occur on the picosecond time scale or faster. PMID:6626668

  20. Transient absorption spectroscopy detection of sensitized delayed fluorescence in chiral benzophenone/naphthalene systems

    NASA Astrophysics Data System (ADS)

    Bonancía, Paula; Jiménez, M. Consuelo; Miranda, Miguel A.

    2011-10-01

    Transient absorption spectroscopy has proven to be a powerful tool to investigate the formation and decay of excited singlet states upon triplet-triplet annihilation, following T-T energy transfer from a selectively excited sensitizer. Thus, upon selective excitation of benzophenone (BZP) by laser flash photolysis (LFP) at λ = 355 nm in the presence of naphthalene (NPT), a negative band centered at 340 nm has been detected, with growth and decay in the microsecond timescale. It has been assigned to the P-type NPT delayed-fluorescence. In the case of chiral BZP/NPT systems, stereodifferentiation has been observed in the kinetics of the involved photophysical processes.

  1. Real-time measurement of dual-wavelength laser-induced fluorescence spectra of individual aerosol particles.

    PubMed

    Huang, Hermes C; Pan, Yong-Le; Hill, Steven C; Pinnick, Ronald G; Chang, Richard K

    2008-10-13

    We report the development of an in-situ aerosol detection system capable of rapidly measuring dual-wavelength laser-induced fluorescence spectra of single particles on the fly using a single spectrometer and a single 32-anode photomultiplier array. We demonstrate the capability of this system with both reference samples and outdoor air. We present spectra from separate excitation wavelengths from the same particle that demonstrate improved discrimination capability compared with only using one excitation wavelength. PMID:18852760

  2. 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.

  3. 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.

  4. Investigation of two-photon absorption properties in new A-D-A compounds emitting blue and yellow fluorescence

    NASA Astrophysics Data System (ADS)

    Jin, Fan; Cai, Zhi-Bin; Huang, Jiu-Qiang; Li, Sheng-Li; Tian, Yu-Peng

    2015-08-01

    Three new acceptor-donor-acceptor compounds (LBQ, DBQ, BYQ) were synthesized and characterized by infrared, hydrogen nuclear magnetic resonance, mass spectrometry and elemental analysis. Their photophysical properties were investigated including linear absorption, single-photon excited fluorescence, fluorescence quantum yield and two-photon absorption. These compounds in CH2Cl2 exhibit good fluorescence quantum yield which are 0.36, 0.26, and 0.25 and the largest two-photon absorption cross-section which are 48, 36, and 181 GM respectively. Under the excitation of Ti: sapphire laser with a pulse width of 140 fs, LBQ and DBQ emit blue two-photon excited fluorescence (TPEF), while BYQ emits bright yellow TPEF. BYQ has a good solubility in water and the σ can be as large as 130 GM, so it shows promising applications in many pharmaceutical and biological fields.

  5. 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.

  6. Analysis of in vivo chlorophyll fluorescence spectra to monitor physiological state of tomato plants growing under zinc stress.

    PubMed

    Cherif, Jaouhra; Derbel, Najoua; Nakkach, Mohamed; Bergmann, Hubertus von; Jemal, Fatma; Lakhdar, Zohra Ben

    2010-12-01

    The effects of zinc (Zn) on plant chlorophyll fluorescence were investigated in 10-day-old tomato (Solanum lycopersicum) seedlings subjected for 7 days to a series of zinc (10, 50, 100 and 150μM) applied via the nutrient solution. The chlorophyll fluorescence spectra of leaves were recorded in the spectral region 650-800nm using the spectroscopic technique of ultraviolet light emitting diode induced fluorescence spectroscopy (UV-LED IFS). These spectra have been used to analyze the effect of several doses of zinc on the photosynthetic activities of tomato plants. The fluorescence intensity ratios (FIR) at the two maxima (F(690)/F(735)) of control as well as treated tomato plants were calculated by evaluating curve-fitted parameters using a Gaussian spectral function. The variable chlorophyll fluorescence decrease ratio (R(Fd)) values were determined from the fluorescence induction kinetics curves recorded at 690nm and 735nm. In addition, Zn accumulation in plants, plant growth, photosynthetic pigments content and malondialdehyde level (MDA, an index of lipid peroxidation) were also estimated. The results indicated that the plants treated with 10μM of zinc exhibited better growth, however, higher concentrations of zinc were harmful for plants. Excess Zn induced a decrease in the R(Fd) values, which was associated with a strong decline of the total chlorophylls content and an increase of MDA level. The total chlorophylls content decline could also be followed via an increase of the chlorophyll fluorescence ratio F(690)/F(735). PMID:20829059

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. A comparison of the fluorescence spectra of murine and bovine central nervous system (CNS) and other tissues

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Here we describe a comparison of the fluorescence spectra of bovine tissues with murine tissues in order to determine whether spectral features are conserved and whether an appropriate and practical laboratory small animal model system could be identified to be used for investigation of tissue and a...

  14. 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.

  15. A New Method for the Determination of Potassium Sorbate Combining Fluorescence Spectra Method with PSO-BP Neural Network.

    PubMed

    Wang, Shu-tao; Chen, Dong-ying; Wang, Xing-long; Wei, Meng; Wang, Zhi-fang

    2015-12-01

    In this paper, fluorescence spectra properties of potassium sorbate in aqueous solution and orange juice are studied, and the result.shows that in two solution there are many difference in fluorescence spectra of potassium sorbate, but the fluorescence characteristic peak exists in λ(ex)/λ(em) = 375/490 nm. It can be seen from the two dimensional fluorescence spectra that the relationship between the fluorescence intensity and the concentration of potassium sorbate is very complex, so there is no linear relationship between them. To determine the concentration of potassium sorbate in orange juice, a new method combining Particle Swarm Optimization (PSO) algorithm with Back Propagation (BP) neural network is proposed. The relative error of two predicted concentrations is 1.83% and 1.53% respectively, which indicate that the method is feasible. The PSO-BP neural network can accurately measure the concentration of potassium sorbate in orange juice in the range of 0.1-2.0 g · L⁻¹. PMID:26964248

  16. Spectral fluorescence signature techniques and absorption measurements for continuous monitoring of biofuel-producing microalgae cultures

    NASA Astrophysics Data System (ADS)

    Martín de la Cruz, M. C.; Gonzalez Vilas, L.; Yarovenko, N.; Spyrakos, E.; Torres Palenzuela, J. M.

    2013-08-01

    Biofuel production from microalgae can be both sustainable and economically viable. Particularly in the case of algal growth in wastewater an extra benefit is the removal or biotransformation of pollutants from these types of waters. A continuous monitoring system of the microalgae status and the concentration of different wastewater contaminants could be of great help in the biomass production and the water characterisation. In this study we present a system where spectral fluorescence signature (SFS) techniques are used along with absorption measurements to monitor microalgae cultures in wastewater and other mediums. This system aims to optimise the microalgae production for biofuel applications or other uses and was developed and tested in prototype indoor photo-bioreactors at the University of Vigo. SFS techniques were applied using the fluorescence analyser INSTAND-SCREENER developed by Laser Diagnostic Instruments AS. INSTAND-SCREENER permits wavelength scanning in two modes, one in UV and another in VIS. In parallel, it permits the on-line monitoring and rapid analysis of both water quality and phytoplankton status without prior treatment of the sample. Considering that different contaminants and microalgae features (density, status etc.) have different spectral signatures of fluorescence and absorption properties, it is possible to characterise them developing classification libraries. Several algorithms were used for the classification. The implementation of this system in an outdoor raceway reactor in a Spanish wastewater treatment plant is also discussed. This study was part of the Project EnerBioAlgae (http://www.enerbioalgae.com/), which was funded by the Interreg SUDOE and led by the University of Vigo.

  17. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes. I. C60, C59N+, and C48N12: theory and experiment.

    PubMed

    Xie, Rui-Hua; Bryant, Garnett W; Sun, Guangyu; Nicklaus, Marc C; Heringer, David; Frauenheim, Th; Manaa, M Riad; Smith, Vedene H; Araki, Yasuyuki; Ito, Osamu

    2004-03-15

    Low-energy excitations and optical absorption spectrum of C(60) are computed by using time-dependent (TD) Hartree-Fock, TD-density functional theory (TD-DFT), TD DFT-based tight-binding (TD-DFT-TB), and a semiempirical Zerner intermediate neglect of diatomic differential overlap method. A detailed comparison of experiment and theory for the excitation energies, optical gap, and absorption spectrum of C(60) is presented. It is found that electron correlations and correlation of excitations play important roles in accurately assigning the spectral features of C(60), and that the TD-DFT method with nonhybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C(60) justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C(59)N(+), to serve as a spectroscopy reference for the characterization of carborane anion salts. Although it is an isoelectronic analogue to C(60), C(59)N(+) exhibits distinguishing spectral features different from C(60): (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C(59)N(+) characterize and explain well the measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C(59)N][Ag(CB(11)H(6)Cl(6))(2)] [Kim et al., J. Am. Chem. Soc. 125, 4024 (2003)]. For the most stable isomer of C(48)N(12), we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C(60), and optical absorption maxima occur at 585, 528, 443, 363, 340, 314, and 303 nm. We point out that the characterization of the UV-vis and transient absorption

  18. 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

  19. Real-time detection and characterization of individual flowing airborne biological particles: fluorescence spectra and elastic scattering measurements

    NASA Astrophysics Data System (ADS)

    Pan, Yongle; Holler, Stephen; Chang, Richard K.; Hill, Steven C.; Pinnick, Ronald G.; Niles, Stanley; Bottiger, Jerold R.; Bronk, Burt V.

    1999-11-01

    Real-time methods which is reagentless and could detect and partially characterize bioaerosols are of current interest. We present a technique for real-time measurement of UV-excited fluorescence spectra and two-dimensional angular optical scattering (TAOS) from individual flowing biological aerosol particles. The fluorescence spectra have been observed from more than 20 samples including Bacillus subtilis, Escherichia coli, Erwinia herbicola, allergens, dust, and smoke. The S/N and resolution of the spectra are sufficient for observing small lineshape differences among the same type of bioaerosol prepared under different conditions. The additional information from TAOS regarding particle size, shape, and granularity has the potential of aiding in distinguishing bacterial aerosols from other aerosols, such as diesel and cigarette smoke.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Single particle size and fluorescence spectra from emissions of burning materials in a tube furnace to simulate burn pits

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Houck, Joshua D. T.; Clark, Pamela A.; Pinnick, Ronald G.

    2013-08-01

    A single-particle fluorescence spectrometer (SPFS) and an aerodynamic particle sizer were used to measure the fluorescence spectra and particle size distribution from the particulate emissions of 12 different burning materials in a tube furnace to simulate open-air burning of garbage. Although the particulate emissions are likely dominated by particles <1 μm diameter, only the spectra of supermicron particles were measured here. The overall fluorescence spectral profiles exhibit either one or two broad bands peaked around 300-450 nm within the 280-650 nm spectral range, when the particles are illuminated with a 263-nm laser. Different burning materials have different profiles, some of them (cigarette, hair, uniform, paper, and plastics) show small changes during the burning process, and while others (beef, bread, carrot, Styrofoam, and wood) show big variations, which initially exhibit a single UV peak (around 310-340 nm) and a long shoulder in visible, and then gradually evolve into a bimodal spectrum with another visible peak (around 430-450 nm) having increasing intensity during the burning process. These spectral profiles could mainly derive from polycyclic aromatic hydrocarbons with the combinations of tyrosine-like, tryptophan-like, and other humic-like substances. About 68 % of these single-particle fluorescence spectra can be grouped into 10 clustered spectral templates that are derived from the spectra of millions of atmospheric aerosol particles observed in three locations; while the others, particularly these bimodal spectra, do not fall into any of the 10 templates. Therefore, the spectra from particulate emissions of burning materials can be easily discriminated from that of common atmospheric aerosol particles. The SFFS technology could be a good tool for monitoring burning pit emissions and possibly for distinguishing them from atmospheric aerosol particles.

  10. 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

  11. 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.

  12. Absorption and fluorescence of hydrophobic components of dissolved organic matter in several Karelian lakes with stratified structures

    NASA Astrophysics Data System (ADS)

    Khundzhua, Daria A.; Kharcheva, Anastasia V.; Krasnova, Elena D.; Gorshkova, Olga M.; Chevel, Kira A.; Yuzhakov, Viktor I.; Patsaeva, Svetlana V.

    2016-04-01

    Hydrophobic components of cromophoric dissolved organic matter (CDOM) extracted from water samples and sediments taken in several relic basins located on Karelian shoreline of the White Sea were analyzed using spectroscopic techniques. Those water reservoirs exist at various stages of isolation from the White Sea and represent complex stratified systems of fresh and marine water layers not completely mixing trough the year. Basins separating from the White Sea are the unique natural objects for investigations of properties CDOM, its transformation in the process of turning the marine ecosystem into freshwater environment. CDOM occurring in all types of natural water represents a significant reservoir of organic carbon and plays a key role in the carbon cycle on the Earth. However, aquatic CDOM and nonliving organic matter in sediments from relic separating basins still have not been studied. The target of this work was to study absorption and fluorescence spectra of hydrophobic components of aquatic CDOM from different water depth and sediments in several separated basins of the Kandalaksha Gulf of the White Sea located near the N.A. Pertsov White Sea Biological Station.

  13. 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.

  14. 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

  15. Electrochemical exfoliation of carbon dots with the narrowest full width at half maximum in their fluorescence spectra in the ultraviolet region using only water as electrolyte.

    PubMed

    Li, Xuehua; Zhao, Zhiwei; Pan, Chen

    2016-08-01

    Here, a novel kind of CDs were electrochemically exfoliated from graphite rods using distilled water as the only electrolyte. The as-exfoliated CDs showed two significant features: the narrowest fluorescence spectra with a FWHM of only 10 nm and ultraviolet fluorescence spectra in the region up to 360 nm. PMID:27376467

  16. Optimization strategies for a fluorescent dye with bimodal excitation spectra: application to semiautomated proteomics

    NASA Astrophysics Data System (ADS)

    Patton, Wayne F.; Berggren, Kiera N.; Lopez, Mary F.

    2001-04-01

    Facilities engaged in proteome analysis differ significantly in the degree that they implement automated systems for high-throughput protein characterization. Though automated workstation environments are becoming more routine in the biotechnology and pharmaceutical sectors of industry, university-based laboratories often perform these tasks manually, submitting protein spots excised from polyacrylamide gels to institutional core facilities for identification. For broad compatibility with imaging platforms, an optimized fluorescent dye developed for proteomics applications should be designed taking into account that laser scanners use visible light excitation and that charge-coupled device camera systems and gas discharge transilluminators rely upon UV excitation. The luminescent ruthenium metal complex, SYPRO Ruby protein gel stain, is compatible with a variety of excitation sources since it displays intense UV (280 nm) and visible (470 nm) absorption maxima. Localization is achieved by noncovalent, electrostatic and hydrophobic binding of dye to proteins, with signal being detected at 610 nm. Since proteins are not covalently modified by the dye, compatibility with downstream microchemical characterization techniques such as matrix-assisted laser desorption/ionization-mass spectrometry is assured. Protocols have been devised for optimizing fluorophore intensity. SYPRO Ruby dye outperforms alternatives such as silver staining in terms of quantitative capabilities, compatibility with mass spectrometry and ease of integration into automated work environments.

  17. Molecular dynamic simulation of EuT -doped sodium borate glasses and their fluorescence spectra

    SciTech Connect

    Hirao, K.; Soga, N.

    1985-10-01

    A molecular dynamic simulation was performed for sodium borate glasses containing a small amount of Eu2O3 to investigate the local structures of cations in glass. A new potential V /SUB B-B/ in the form -A exp (-C(r - 0.239)S) was added to the regular modified Born-Mayer-Huggins-type potentials, /PHI/ /SUB B-B/ , /PHI/ /SUB B-O/ , and /PHI/ /SUB O-O/ , to account for the directional tendency of the borate network structure. With this potential added, both the radial distribution of sodium borate glasses observed by smallangle X-ray diffraction and the change in coordination number of boron with sodium content obtained by NMR agreed well with the simulation. The average coordination number of EuT ions in the simulated glasses varied from 7.5 to 8.6, depending on the composition of the host sodium borate glasses. The inhomogeneous line width of the VD0-XF2 emission peak also changed, depending on the sodium content, with a maximum at 18 mol % Na2O content; this result agrees well with experimental data obtained from laser-induced fluorescence spectra.

  18. Insitu measurements of laser-induced-fluorescence spectra of single atmospheric organic carbon aerosol particles for their partial classification. (Invited)

    NASA Astrophysics Data System (ADS)

    Pinnick, R. G.; Pan, Y.; Hill, S.; Rosen, J. M.; Chang, R. K.

    2009-12-01

    Aerosols are ubiquitous in the earth’s atmosphere. Within the last two decades, the importance of organic carbon aerosols (OCAs) has been widely recognized. OCAs have both natural and anthropogenic sources and have effects ranging from atmospheric radiative forcing to human health. Improved methods for measuring and classifying OCAs are needed for better understanding their sources, transformation, and fate. In this talk we focus on the use of a relatively new technique for characterization of single OCA particles in atmospheric aerosol: ultraviolet laser-induced-fluorescence (UV-LIF). UV-LIF spectra of atmospheric aerosols measured at multiple sites with different regional climate (Adelphi, MD, New Haven, CT, and Las Cruces, NM) are reported. A hierarchical clustering method was used to cluster (approximately 90%) of the single-particle UV-LIF spectra into 8-10 groups (clusters). Some of these clusters have spectra that are similar to spectra of some important classes of atmospheric aerosol, such as humic/fulvic acids and humic-like substances, bacteria, cellulose, marine aerosol, and polycyclic aromatic hydrocarbons. The most highly populated clusters, and some of the less populated ones, appear at all sites. On average, spectra characteristic of humic/fulvic acids and humic-like-substances (HULIS) comprise 28-43% of fluorescent particles at all three sites; whereas cellulose-like spectra contribute only 1-3%.

  19. 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

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

    NASA Astrophysics Data System (ADS)

    Stevens, Michael H.

    1995-08-01

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

  1. Near infrared excited micro-Raman spectra of 4:1 methanol-ethanol mixture and ruby fluorescence at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, X. B.; Shen, Z. X.; Tang, S. H.; Kuok, M. H.

    1999-06-01

    Near infrared (NIR) lasers, as a new excitation source for Raman spectroscopy, has shown its unique advantages and is being increasingly used for some special samples, such as those emitting strong fluorescence in the visible region. This article focuses on some issues related to high-pressure micro-Raman spectroscopy using NIR excitation source. The Raman spectra of 4:1 methanol-ethanol mixture (4:1 M-E) show a linear variation in both Raman shifts and linewidths under pressure up to 18 GPa. This result is useful in distinguishing Raman scattering of samples from that of the alcohol mixture, an extensively used pressure-transmitting medium. The R1 fluorescence in the red region induced by two-photon absorption of the NIR laser is strong enough to be used as pressure scale. The frequency and line width of the R1 lines are very sensitive to pressure change and the glass transition of the pressure medium. Our results manifest that it is reliable and convenient to use NIR induced two-photon excited fluorescence of ruby for both pressure calibration and distribution of pressure in the 4:1 M-E pressure transmitting medium.

  2. 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

  3. 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.

  4. Potential chlorofluorocarbon replacements: OH reaction rate constants between 250 and 315 K and infrared absorption spectra

    SciTech Connect

    Garland, N.L.; Medhurst, L.J.; Nelson, H.H.

    1993-12-20

    The authors measured the rate constant for reactions of the OH radical with several potential chlorofluorocarbon replacements over the temperature range 251-314 K using laser photolysis laser-induced fluorescence techniques. The compounds studied and Arrhenius parameters determined from fits to the measured rate constants are as follows: CHF{sub 2}OCHF{sub 2} (E 134), k(T) = (5.4 {+-} 3.5) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}3.1 {+-} 0.4 kcal mol{sup {minus}1})/RT]; CF{sub 3}CH{sub 2}CF{sub 3} (FC 236fa), k(T) = (2.0 {+-} 1.0) x 10{sup {minus}14} cm{sup 3} s{sup {minus}1} exp [({minus}1.8 {+-} 0.3 kcal mol{sup {minus}1})/RT]; CF{sub 3}CHFCHF{sub 2} (FC 236ea), k(T) = (2.0 {+-} 0.9) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.0 {+-} 0.3 kcal mol{sup {minus}1})/RT]; and CF{sub 3}CF{sub 2}CH{sub 2}F (FC 236cb), k(T) = (2.6 {+-} 1.6) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.2 {+-} 0.4 kcal mol{sup {minus}1})/RT]. The measured activation energies (2-3 kcal mol{sup {minus}1}) are consistent with a mechanism of H atom abstraction. The tropospheric lifetimes, estimated from the measured OH reaction rates, and measured integrated infrared absorption cross sections over the range 770 to 1430 cm{sup {minus}1} suggest that E 134 and FC 236fa may have significant global warming potential, while FC 236ea and FC 236cb do not. 17 refs., 4 figs., 3 tabs.

  5. Invited Review Article: Imaging techniques for harmonic and multiphoton absorption fluorescence microscopy

    PubMed Central

    Carriles, Ramón; Schafer, Dawn N.; Sheetz, Kraig E.; Field, Jeffrey J.; Cisek, Richard; Barzda, Virginijus; Sylvester, Anne W.; Squier, Jeffrey A.

    2009-01-01

    We review the current state of multiphoton microscopy. In particular, the requirements and limitations associated with high-speed multiphoton imaging are considered. A description of the different scanning technologies such as line scan, multifoci approaches, multidepth microscopy, and novel detection techniques is given. The main nonlinear optical contrast mechanisms employed in microscopy are reviewed, namely, multiphoton excitation fluorescence, second harmonic generation, and third harmonic generation. Techniques for optimizing these nonlinear mechanisms through a careful measurement of the spatial and temporal characteristics of the focal volume are discussed, and a brief summary of photobleaching effects is provided. Finally, we consider three new applications of multiphoton microscopy: nonlinear imaging in microfluidics as applied to chemical analysis and the use of two-photon absorption and self-phase modulation as contrast mechanisms applied to imaging problems in the medical sciences. PMID:19725639

  6. New Approaches for Correction of Interlayer Absorption Effects in X-ray Fluorescence Imaging of Paintings.

    PubMed

    Wróbel, Paweł M; Frączek, Piotr; Lankosz, Marek

    2016-02-01

    The X-ray fluorescence imaging technique allows not only the imaging itself but also the identification of the hidden paint layers what makes it much more versatile as compared with X-ray radiography. One of the main disadvantages of the former method is the fact that the characteristic X-rays from the deeper paint layers are absorbed in the covering layers. This effect is manifested by some artifacts that impede a proper interpretation of the acquired images. In this work, it is shown that the methodology for correction of the interlayer absorption effects can be extended to the case of polychromatic excitation. Additionally, a new approach for determination of the optimal correction parameters has also been presented. The methodology was verified using either the test painting or the mock-up painting both measured with a table-top micro-XRF setup. PMID:26708500

  7. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate.

    PubMed

    Obukhova, Elena N; Mchedlov-Petrossyan, Nikolay O; Vodolazkaya, Natalya A; Patsenker, Leonid D; Doroshenko, Andrey O; Marynin, Andriy I; Krasovitskii, Boris M

    2017-01-01

    Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR(+)⇄R+H(+)) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions. In this media, the form R exists as a zwitterion R(±). The indices of apparent ionization constants of fifteen rhodamine cations HR(+) with different substituents in the xanthene moiety vary within the range of pKa(app)=5.04 to 5.53. The distinct dependence of emission of rhodamines bound to micelles on pH of bulk water opens the possibility of using them as fluorescent interfacial acid-base indicators. PMID:27423469

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide

    NASA Astrophysics Data System (ADS)

    Holloway, John S.; Jakoubek, Roger O.; Parrish, David D.; Gerbig, Christoph; Volz-Thomas, Andreas; Schmitgen, Sandra; Fried, Alan; Wert, Brian; Henry, Bruce; Drummond, James R.

    2000-01-01

    During the fall 1997 North Atlantic Regional Experiment (NARE 97), two separate intercomparisons of aircraft-based carbon monoxide measurement instrumentation were conducted. On September 2, CO measurements were simultaneously made aboard the National Oceanic and Atmospheric Administration (NOAA) WP-3 by vacuum ultraviolet (VUV) fluorescence and by tunable diode laser absorption spectroscopy (TDLAS). On September 18, an intercomparison flight was conducted between two separate instruments, both employing the VUV fluorescence method, on the NOAA WP-3 and the U.K. Meteorological Office C-130 Hercules. The results indicate that both of the VUV fluorescence instruments and the TDLAS system are capable of measuring ambient CO accurately and precisely with no apparent interferences in 5 s. The accuracy of the measurements, based upon three independent calibration systems, is indicated by the agreement to within 11% with systematic offsets of less than 1 ppbv. In addition, one of the groups participated in the Measurement of Air Pollution From Satellite (MAPS) intercomparison [Novelli et al., 1998] with a different measurement technique but very similar calibration system, and agreed with the accepted analysis to within 5%. The precision of the measurements is indicated by the variability of the ratio of simultaneous measurements from the separate instruments. This variability is consistent with the estimated precisions of 1.5 ppbv and 2.2 ppbv for the 5 s average results of the C-130 and the WP-3 instruments, respectively, and indicates a precision of approximately 3.6% for the TDLAS instrument. The excellent agreement of the instruments in both intercomparisons demonstrates that significant interferences in the measurements are absent in air masses that ranged from 7 km in the midtroposphere to boundary layer conditions including subtropical marine air and continental outflow with embedded urban plumes. The intercomparison of the two VUV instruments that differed widely

  13. Fluorescent spectra of tunable infrared laser crystals based on Cr/sup 3 +/ in oxides of high-valence cations

    SciTech Connect

    Luo Zun-Du; Chen Chih-Ming; Chen Dao

    1986-10-01

    Fluorescent spectra and lifetimes have been measured for trivalent chromium ions in KAl(MoO/sub 4/)/sub 2/, Al/sub 2/(WO/sub 4/)/sub 3/, AlNbO/sub 4/, and AlTaO/sub 4/. Because of the polarization effects of the high-valence cations, the crystal fields of the chromium ions have been reduced. Hence the T/sub 2/--/sup 4/A/sub 2/ vibronic transition spectral-peak wavelengths are longer than 800 nm. Because of their strong electron-phonon coupling interactions and rather broad fluorescent peaks, these materials may be useful as tunable infrared laser crystals.

  14. 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.

  15. 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.

  16. Heavy Metals Effect on Cyanobacteria Synechocystis aquatilis Study Using Absorption, Fluorescence, Flow Cytometry, and Photothermal Measurements

    NASA Astrophysics Data System (ADS)

    Dudkowiak, A.; Olejarz, B.; Łukasiewicz, J.; Banaszek, J.; Sikora, J.; Wiktorowicz, K.

    2011-04-01

    The toxic effect of six heavy metals on cyanobacteria Synechocystis aquatilis was studied by absorption, fluorescence, flow cytometry, and photothermal measurements. This study indicates that at the concentration used, the cyanobacteria are more sensitive to silver, copper, and mercury than to cadmium, lead, and zinc metals. Disregarding the decrease in the yields of the related radiative processes caused by photochemical processes and/or damage to phycobilisomes, no changes were detected in the efficiency of thermal deactivation processes within a few microseconds, which can indicate the lack of disturbances in the photosynthetic light reaction and the lack of damage to the photosystem caused by the heavy metal ions in the concentrations used. The results demonstrate that the relative values of fluorescence yield as well as promptly generated heat calculated for the metal-affected and unaffected (reference) bacteria are sensitive indicators of environmental pollution with heavy metal ions, whereas the complementary methods proposed could be used as a noninvasive and fast procedure for in vivo assessment of their toxicity.

  17. Determination of mercury distribution inside spent compact fluorescent lamps by atomic absorption spectrometry

    SciTech Connect

    Rey-Raap, Natalia

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer New treatments for CFL are required considering the aim of Directive 202/96/CE. Black-Right-Pointing-Pointer It is shown that most of the mercury introduced into a CFL is in the phosphor powder. Black-Right-Pointing-Pointer Experimental conditions for microwave-assisted sample digestion followed by AAS measurements are described. Black-Right-Pointing-Pointer By washing the glass it is possible to reduce the concentration below legal limits. - Abstract: In this study, spent compact fluorescent lamps were characterized to determine the distribution of mercury. The procedure used in this research allowed mercury to be extracted in the vapor phase, from the phosphor powder, and the glass matrix. Mercury concentration in the three phases was determined by the method known as cold vapor atomic absorption spectrometry. Median values obtained in the study showed that a compact fluorescent lamp contained 24.52 {+-} 0.4 ppb of mercury in the vapor phase, 204.16 {+-} 8.9 ppb of mercury in the phosphor powder, and 18.74 {+-} 0.5 ppb of mercury in the glass matrix. There are differences in mercury concentration between the lamps since the year of manufacture or the hours of operation affect both mercury content and its distribution. The 85.76% of the mercury introduced into a compact fluorescent lamp becomes a component of the phosphor powder, while more than 13.66% is diffused through the glass matrix. By washing and eliminating all phosphor powder attached to the glass surface it is possible to classified the glass as a non-hazardous waste.

  18. 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.

  19. 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.

  20. Describing two-photon absorptivity of fluorescent proteins with a new vibronic coupling mechanism.

    PubMed

    Drobizhev, M; Makarov, N S; Tillo, S E; Hughes, T E; Rebane, A

    2012-02-01

    Fluorescent proteins (FPs) are widely used in two-photon microscopy as genetically encoded probes. Understanding the physical basics of their two-photon absorption (2PA) properties is therefore crucial for creation of two-photon brighter mutants. On the other hand, it can give us better insight into molecular interactions of the FP chromophore with a complex protein environment. It is known that, compared to the one-photon absorption spectrum, where the pure electronic transition is the strongest, the 2PA spectrum of a number of FPs is dominated by a vibronic transition. The physical mechanism of such intensity redistribution is not understood. Here, we present a new physical model that explains this effect through the "Herzberg-Teller"-type vibronic coupling of the difference between the permanent dipole moments in the ground and excited states (Δμ) to the bond-length-alternating coordinate. This model also enables us to quantitatively describe a large variability of the 2PA peak intensity in a series of red FPs with the same chromophore through the interference between the "Herzberg-Teller" and Franck-Condon terms. PMID:22224830

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. Diagnostics of a see-through hollow cathode discharge by emission, absorption, and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Taylor, Nicholas

    Atomic line filters have been suggested to be attractive in areas of Doppler velocimetry, resonance fluorescence detection, and resonance ionization detection. They are based on the resonant absorption of photons by an atomic vapor, and allow all other radiation to pass. This allows the detection of very low levels of light superimposed on a large optical background. Several elements have been studied for use as atomic line filters, such as the alkali metals, alkaline earths, and thallium. As previously recognized, thallium is especially attractive since the 535.046 nm metastable transition overlaps with the second harmonic output of an Nd:La2Be2O 5 (BEL) laser (1070 nm). This makes thallium ideal for certain applications as an atomic line filter. Recently a see-through hollow cathode lamp, or galvatron (Hamamatsu), was made commercially available. The galvatron geometry is unique compared to traditional hollow cathode lamps since the cathode and cell are oriented in a T-shape, with the cathode bored completely through to allow the propagation of a light source through the cathode. This allows multi-step excitation of the atomic vapor, not easily accomplished with a traditional hollow cathode lamp. The advantages that a galvatron offers over conventional atomic reservoirs make it an attractive candidate for the application as an atomic line filter; however, little spectroscopic data have been found in the literature. For this reason, Doppler temperatures, number densities, quantum efficiencies, and lifetimes have been determined in order to characterize this atomic reservoir as a potential atomic line filter. These parameters are determined by use of various spectroscopic techniques which include emission, absorption, time-resolved fluorescence, and time-resolved laser-induced saturated fluorescence spectroscopy. From these measurements, it has been demonstrated that a galvatron is an attractive atomic reservoir for applications as an atomic line filter. The

  7. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes: I. C60, C59N+ and C48N12

    SciTech Connect

    Xie, R; Bryant, G W; Sun, G; C.Nicklaus, M; Heringer, D; Frauenheim, T; Manaa, M R; Smith, Jr., V H; Araki, Y; Ito, O

    2003-10-02

    Low-energy excitations and optical absorption spectrum of C{sub 60} are computed by using time-dependent (TD) Hartree-Fock (HF), TD-density functional theory (TD-DFT), TD-DFT-based tight-binding (TD-DFT-TB) and a semiempirical ZINDO method. A detailed comparison of experiment and theory for the excitation energies, optical gap and absorption spectrum of C{sub 60} is presented. It is found that electron correlations and collective effects of exciton pairs play important roles in assigning accurately the spectral features of C{sub 60} and the TD-DFT method with non-hybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C{sub 60} justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C{sub 59}N{sup +} exhibits distinguishing spectral features different from C{sub 60}: (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C{sub 59}N{sup +} characterize and explain well our measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C{sub 59}N][Ag(CB{sub 11}H{sub 6}Cl{sub 6}){sub 2}]. For the most stable isomer of C{sub 48}N{sub 12}, we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C{sub 60}, and optical absorption maxima occur at 585, 528, 443, 363, 340, 314 and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C{sub 48}N{sub 12} isomers is helpful in distinguishing the isomer structures required for applications in molecular electronics. For C{sub 59}N{sup +} and C{sub 48}N

  8. Using violet laser-induced chlorophyll fluorescence emission spectra for crop yield assessment of cowpea (Vigna unguiculata (L) Walp) varieties

    NASA Astrophysics Data System (ADS)

    Anderson, Benjamin; Buah-Bassuah, Paul K.; Tetteh, Jonathan P.

    2004-07-01

    The use of violet laser-induced chlorophyll fluorescence (LICF) emission spectra to monitor the growth of five varieties of cowpea in the University of Cape Coast Botanical Garden is presented. Radiation from a continuous-wave violet laser diode emitting at 396 nm through a fibre is closely incident on in vivo leaves of cowpea to excite chlorophyll fluorescence, which is detected by an integrated spectrometer with CCD readout. The chlorophyll fluorescence spectra with peaks at 683 and 731 nm were used for growth monitoring of the cowpea plants over three weeks and analysed using Gaussian spectral functions with curve fitted parameters to determine the peak positions, area under the spectral curve and the intensity ratio F683/F731. The variation in the intensity ratio of the chlorophyll bands showed sensitive changes indicating the photosynthetic activity of the cowpea varieties. A discussion of the fluorescence result as compared to conventional assessment is presented with regard to discrimination between the cowpea varieties in terms of crop yield performance.

  9. 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.

  10. Intrinsic fluorescence spectra characteristics of vitamin B1, B2, and B6

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Xiao, Xue; Zhao, Xuesong; Hu, Lan; Lv, Caofang; Yin, Zhangkun

    2015-11-01

    This paper presents the intrinsic fluorescence characteristics of vitamin B1, B2 and B6 measured with 3D fluorescence Spectrophotometer. Three strong fluorescence areas of vitamin B2 locate at λex/λem=270/525nm, 370/525nm and 450/525nm, one fluorescence areas of vitamin B1 locates at λex/λem=370/460nm, two fluorescence areas of vitamin B6 locates at λex/λem=250/370nm and 325/370nm were found. The influence of pH of solution to the fluorescence profile was also discussed. Using the PARAFAC algorithm, 10 vitamin B1, B2 and B6 mixed solutions were successfully decomposed, and the emission profiles, excitation profiles, central wavelengths and the concentration of the three components were retrieved precisely through about 5 iteration times.

  11. Environmentally friendly Zn0.75Cd0.25S/PVA heterosystem nanocomposite: UV-stimulated emission and absorption spectra

    NASA Astrophysics Data System (ADS)

    Imam, N. G.; Mohamed, Mohamed Bakr

    2016-02-01

    Zn0.75Cd0.25S nanoparticles prepared at different temperatures were composited with polyvinyl alcohol for functionalization it in wide spectrum of applications such as in photocatalysis. The nanostructure of the Zn0.75Cd0.25S mother phase is confirmed by X-ray diffraction in addition to absorption and fluorescence spectra. UV/VIS. measurements show that, the transmittance coefficient of Zn0.75Cd0.25S/PVA nanocomposite is lesser than that of pure PVA by 0.33% and varies upon increasing the preparation temperature; reaching a maximum value for the sample prepared at 300 °C. It was found that the optical band gap tunes with annealing temperature which, in turns, with particle size. The refractive index of the Zn0.75Cd0.25S/PVA nanocomposite films decrease with increasing wavelength and saturates at high wavelengths. The optical conductivity increases with increasing photon energy which may be due to the excitation of electrons by photon energy. The optical conductivity of Zn0.75Cd0.25S/PVA nanocomposite is lesser than that of pure PVA and it decreases as the preparation temperature of Zn0.75Cd0.25S nanoparticles in PVA matrix increases which could be related to the decrease in the extinction coefficient and the density of localized states in the gap. Abroad peak deconvoluted, by Gaussian fitting function, into two violet and blue colors was observed in the fluorescence spectra under UV light irradiation. The two emission bands are attributed to band edge emission and neutral oxygen vacancies respectively. Analysis of fluorescence (FL) spectra reveals quenching in FL intensity and a peak shifting towards the lower wavelength side with increasing the preparation temperature of the mother phase. The results suggest that the 200 °C Zn0.75Cd0.25S/PVA nanocomposites have been regarded as a promising candidate in many technical fields, such as photocatalytic hydrogen production and/or photocatalytic degradation of organic dyes under UV irradiation due to its high optical

  12. 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

  13. A benzo-15-crown-5-modifying ratiometric-absorption and fluorescent OFF-ON chemosensor for Cu(2.).

    PubMed

    Chen, Yuting; Wang, Xinxin; Wang, Kaili; Zhang, Xiuling

    2016-05-15

    One new benzo-15-crown-5-modifying fluorene Schiff base (FBC), together with the CN-linked fluorene-3,4-dimethoxybenzene (FBDMO) and fluorene-benzene (FB) references, has been designed and facilely synthesized. The binding of Cu(2+) with nitrogen atom of CN moiety in these three compounds can inhibit the photo-induced electronic transition process and induce the ratiometric-absorption and fluorescent OFF-ON response to Cu(2+). Whereas the employment of benzo-15-crown-5 moiety in FBC as additional binding platform for Cu(2+) not only amplifies the fluorescent enhancement of FBCvia preventing the isomerization of CN moiety, but also endows this compound high selectivity and rapid response towards Cu(2+) over the references FB and FBDMO. These results render FBC highly sensitive ratiometric-absorption and fluorescent OFF-ON detecting potential for Cu(2+) with the detection limit of 3.91×10(-6)M. PMID:26971023

  14. A benzo-15-crown-5-modifying ratiometric-absorption and fluorescent OFF-ON chemosensor for Cu2 +

    NASA Astrophysics Data System (ADS)

    Chen, Yuting; Wang, Xinxin; Wang, Kaili; Zhang, Xiuling

    2016-05-01

    One new benzo-15-crown-5-modifying fluorene Schiff base (FBC), together with the Cdbnd N-linked fluorene-3,4-dimethoxybenzene (FBDMO) and fluorene-benzene (FB) references, has been designed and facilely synthesized. The binding of Cu2 + with nitrogen atom of Cdbnd N moiety in these three compounds can inhibit the photo-induced electronic transition process and induce the ratiometric-absorption and fluorescent OFF-ON response to Cu2 +. Whereas the employment of benzo-15-crown-5 moiety in FBC as additional binding platform for Cu2 + not only amplifies the fluorescent enhancement of FBCvia preventing the isomerization of Cdbnd N moiety, but also endows this compound high selectivity and rapid response towards Cu2 + over the references FB and FBDMO. These results render FBC highly sensitive ratiometric-absorption and fluorescent OFF-ON detecting potential for Cu2 + with the detection limit of 3.91 × 10- 6 M.

  15. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra

    PubMed Central

    Goun, Alexei; Bondar, Denys I.; Er, Ali O.; Quine, Zachary; Rabitz, Herschel A.

    2016-01-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters. PMID:27181496

  16. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra.

    PubMed

    Goun, Alexei; Bondar, Denys I; Er, Ali O; Quine, Zachary; Rabitz, Herschel A

    2016-01-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters. PMID:27181496

  17. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra

    NASA Astrophysics Data System (ADS)

    Goun, Alexei; Bondar, Denys I.; Er, Ali O.; Quine, Zachary; Rabitz, Herschel A.

    2016-05-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters.

  18. 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

  19. Nonlinear reconstruction of absorption and fluorescence contrast from measured diffuse transmittance and reflectance of a compressed-breast-simulating phantom

    SciTech Connect

    Ziegler, Ronny; Nielsen, Tim; Koehler, Thomas; Grosenick, Dirk; Steinkellner, Oliver; Hagen, Axel; Macdonald, Rainer; Rinneberg, Herbert

    2009-08-20

    We report on the nonlinear reconstruction of local absorption and fluorescence contrast in tissuelike scattering media from measured time-domain diffuse reflectance and transmittance of laser as well as laser-excited fluorescence radiation. Measurements were taken at selected source-detector offsets using slablike diffusely scattering and fluorescent phantoms containing fluorescent heterogeneities. Such measurements simulate in vivo data that would be obtained employing a scanning, time-domain fluorescence mammograph, where the breast is gently compressed between two parallel glass plates, and source and detector optical fibers scan synchronously at various source-detector offsets, allowing the recording of laser and fluorescence mammograms. The diffusion equations modeling the propagation of the laser and fluorescence radiation were solved in frequency domain by the finite element method simultaneously for several modulation frequencies using Fourier transformation and preprocessed experimental data. To reconstruct the concentration of the fluorescent contrast agent, the Born approximation including higher-order reconstructed photon densities at the excitation wavelength was used. Axial resolution was determined that can be achieved by various detection schemes. We show that remission measurements increase the depth resolution significantly.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Fluorescence excitation and emission spectra of ALA-induced protoporphyrin IX in normal and tumoral tissue of the human bladder

    NASA Astrophysics Data System (ADS)

    Forrer, Martin; Glanzmann, Thomas M.; Mizeret, Jerome C.; Braichotte, Daniel; Wagnieres, Georges A.; van den Bergh, Hubert; Jichlinski, Patrice; Leisinger, Hans-Juerg

    1995-01-01

    In vivo spectrofluorometric analysis represents a tool to obtain information about fluorophore distribution in tissue. Based on a Peltier-cooled CCD we designed a fluorescence excitation and emission spectrograph which allows to obtain tissue spectra endoscopically and in a clinical environment. Clinical studies were performed on patients with positive cytology or tumor recurrence in the urinary bladder. Patients received a 50 ml instillation of 3% ALA solution at pH 5.5 during 3 to 4 hours and underwent a normal white light cystoscopic examination together with light induced fluorescence photodetection at 5 to 8 hours after the beginning of the instillation. Local fluorescence measurements with a single fiber were performed before photodetection. These showed fluorescence ratios between tumor and normal tissue of 1.5 to 20 with the strongest ratios for exophytic papillary tumors. Fluorescence excitation between 380 nm and 450 nm revealed that the higher Protoporphyrin IX (PPIX) signal on tumor tissue is accompanied by a decrease of the autofluorescence at the emission wavelength of 500 nm.

  5. Liquid helium cryostat with internal fluorescence detection for x-ray absorption studies in the 2-6 keV energy region

    NASA Astrophysics Data System (ADS)

    McFarlane Holman, Karen L.; Latimer, Matthew J.; Yachandra, Vittal K.

    2004-06-01

    X-ray absorption spectroscopy (XAS) in the intermediate x-ray region (2-6 keV) for dilute biological samples has been limited because of detector/flux limitations and inadequate cryogenic instrumentation. We have designed and constructed a new tailpiece/sample chamber for a commercially available liquid helium cooled cryostat which overcomes difficulties related to low fluorescence signals by using thin window materials and incorporating an internal photodiode detector. With the apparatus, XAS data at the Cl, S, and Ca K edges have been collected on frozen solutions and biological samples at temperatures down to 60 K. A separate chamber has been incorporated for collecting room-temperature spectra of standard compounds (for energy calibration purposes) which prevents contamination of the cryostat chamber and allows the sample to remain undisturbed, both important concerns for studying dilute and radiation-sensitive samples.

  6. 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

  7. 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

  8. 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

  9. Fluorescence Excitation Spectra of Photo-Fragmented Nitrobenzene Using a Picosecond Laser: Potential Evidence for no Produced by Two Distinct Channels.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Reeve, Scott W.; Allen, Susan D.

    2013-06-01

    Upon absorption of a UV photon, nitrobenzene can dissociate into C_6H_5O and NO through two different mechanisms. Evidence for these mechanisms was obtained from velocity map imaging (VMI) studies and theoretical calculations. VMI experiments showed NO produced with two distinct rotational distributions, which the calculations explained as a fast and a slow channel for NO production. We have recorded high resolution fluorescence excitation spectra of the NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈ 15 ps) by means of a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene while photons of a different energy probed the A^2Σ^+← X^2Π_{(1/2,3/2)} NO band system between 225-260 nm. This laser system allowed us to vary the delay between the photolysis and excitation pulses. At longer delays (>1 ns), we observed an increase in the population of NO, which may be evidence that at least two photolysis channels produce NO. We present the spectra we recorded at various photolysis/probe delays ranging from 0.025 to 1.5 ns. The spectral subtraction method we used to observe the production increase is introduced. Hause, M. L.; Herath, N.; Zhu, R.; Lin, M. C. and Suits, A. G. Nat Chem, Nature Publishing Group, 2011, 3, 932-937

  10. 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.

  11. 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

  12. 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.

  13. 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+.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. A multi-channel monolithic Ge detector system for fluorescence x-ray absorption spectroscopy

    SciTech Connect

    Bucher, J.J.; Allen, P.G.; Edelstein, N.M.; Shuh, D.K.; Madden, N.W.; Cork, C.; Luke, P.; Pehl, D.; Malone, D.

    1995-03-01

    Construction and performance of a monolithic quad-pixel Ge detector for fluorescence x-ray absorption spectroscopy (XAS) at synchrotron radiation sources are described. The detector semiconductor element has an active surface area of 4.0 cm{sup 2} which is electrically separated into four 1.0 cm{sup 2} pixels, with little interfacial dead volume. Spatial response of the array shows that cross-talk between adjacent pixels is < 10% for 5.9 keV photons that fall within 0.5 mm of the pixel boundaries. The detector electronics system uses pre-amplifiers built at LBNL with commercial Tennelec Model TC 244 amplifiers. Using an {sup 55}Fe test source (MnK{sub {alpha}}, 5.9 keV), energy resolution of better than 200 eV is achieved with a 4 {mu}sec peaking time. At 0.5 {mu}sec peaking time, pulse pileup results in a 75% throughput efficiency for an incoming count rate of 100 kHz. Initial XAS fluoresncece measurements at the beamline 4 wiggler end stations at SSRL show that the detector system has several advantages over commercial x-ray spectrometers for low-concentration counting.

  20. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

  1. 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

  2. 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}.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Saturable absorption dynamics in the triplet system and triplet excitation induced singlet fluorescence of some organic molecules

    NASA Astrophysics Data System (ADS)

    Gratz, H.; Penzkofer, A.

    2001-01-01

    The triplet saturable absorption behaviour of the xanthene dyes eosin Y, erythrosin B, and rose bengal and of the fullerene molecule C 70 is studied. The molecules are excited to the S 1-state by intense picosecond pulses (wavelength λP=527 nm). They relax dominantly to the triplet system by intersystem crossing. The triplet-triplet saturable absorption is investigated with time-delayed intense picosecond pulses (wavelength λL=1054 nm) in the transparency region of the molecules in the singlet ground state. Higher excited-state triplet absorption cross-sections and higher excited-state triplet relaxation times are determined by numerical simulation of the experimental results. Time-resolved fluorescence measurements reveal higher excited-state triplet to singlet back-intersystem-crossing and multi-step triplet photoionization. Additionally the two-photon absorption cross-sections at λL=1054 nm are determined by measurement of the fundamental pulse two-photon induced fluorescence relative to the second-harmonic pulse single-photon induced fluorescence.

  10. 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.

  11. 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)

  12. 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.

  13. Saturable absorption and two-photon absorption of 1,2,5-thiadiazolo[3,4-g]quinoxaline based derivatives with near-infrared fluorescence

    NASA Astrophysics Data System (ADS)

    Du, Yabing; Lin, Xiaodong; Jia, Tingjian; Dong, Jun

    2015-03-01

    Organic molecules with near-infrared (NIR) fluorescence are extremely interesting for the applications in nonlinear optical devices and bioimaging. However, such kind of materials have been relatively rarely studied. In this work, the nonlinear optical properties of 1,2,5-thiadiazolo[3,4-g]quinoxaline based derivatives with NIR fluorescence emission have been investigated for the first time. Under the excitation of femtosecond pulses at 532 nm, the chromophore with dithienyl as donor (TQ2) presents saturable absorption (SA) behavior, while no SA has been observed in the derivative with biphenyl (TQ1) as donor. Moreover, TQ2 exhibits much larger two-photon absorption (TPA) cross-sections with strong NIR fluorescence in the second biological window. The larger nonlinear optical properties of TQ2 is due to the introduction of stronger electron-donating group (dithienyl) and the resultant enhanced intramolecular charge transfer properties. At the end, TPA based optical limiting behaviors of the molecules are demonstrated in THF solutions, thanks to their large solubility and strong TPA.

  14. 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

  15. Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Wilkinson, F.; Worrall, D. R.; Ferreira, L. F. Vieira

    1992-02-01

    Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10 6mol -1g. At low loadings of acridine orange on cellulose (<1 μmol g -1) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these "diluted" samples. However, at higher loadings (>20 μmol g -1), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.

  16. 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

  17. Synthesis, structure, infrared and fluorescence spectra of new rare earth complexes with 6-hydroxy chromone-3-carbaldehyde benzoyl hydrazone

    NASA Astrophysics Data System (ADS)

    Wang, Bao-Dui; Yang, Zheng-Yin; Zhang, Ding-Wa; Wang, Yan

    2006-01-01

    A novel 6-hydroxy chromone-3-carbaldehyde benzoyl hydrazone ligand and its four complexes, [LnL2(NO3)2]NO3 [Ln = Eu(1), Sm(2), Tb(3), Dy(4)], were synthesized. The complexes were characterized by the elemental analyses, molar conductivity and IR spectra. The crystal and molecular structure of Sm(III) complex was determined by single-crystal X-ray diffraction: crystallized in the triclinic system, space group P-1, Z = 1, a = 11.037(4) Å, b = 14.770(5) Å, c = 15.032(7) Å, α = 60.583(4), β = 75.528(7), γ = 88.999(4), R1 = 0.0349. The fluorescence properties of complexes in the solid state and in the organic solvent were studied in detail, respectively. Under the excitation of ultraviolet light, strong red fluorescence of solid europium complex was observed. But the green fluorescence of solid terbium complex was not observed. These observations show that the ligand favor energy transfers to the emitting energy level of Eu3+. Some factors that influence the fluorescent intensity were also discussed.

  18. 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…

  19. High-speed laser-induced fluorescence and spark plug absorption sensor diagnostics for mixing and combustion studies in engines.

    PubMed

    Cundy, Michael; Schucht, Torsten; Thiele, Olaf; Sick, Volker

    2009-02-01

    Simultaneous high-speed in-cylinder measurements of laser-induced fluorescence of biacetyl as a fuel tracer and mid-infrared broadband absorption of fuel and combustion products (water and carbon dioxide) using a spark plug probe are compared in an optical engine. The study addresses uncertainties and the applicability of absorption measurements at a location slightly offset to the spark plug when information about mixing at the spark plug is desired. Absorbance profiles reflect important engine operation events, such as valve opening and closing, mixing, combustion, and outgassing from crevices. PMID:19183588

  20. 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.