A best-case probe, light source, and database for H2O absorption thermometry to 2100 K and 50 bar

NASA Astrophysics Data System (ADS)

Brittelle, Mack S.

This work aspired to improve the ability of forthcoming researchers to utilize near IR H2O absorption spectroscopy for thermometry with development of three best-case techniques: the design of novel high temperature sapphire optical access probes, the construction of a fixed-wavelength H 2O absorption spectroscopy system enhanced by an on-board external-cavity diode laser, and the creation of an architecture for a high-temperature and -pressure H2O absorption cross-section database. Each area's main goal was to realize the best-case for direct absorption spectroscopy H2O vapor thermometry at combustion conditions. Optical access to combustion devices is explored through the design and implementation of two versions of novel high-temperature (2000 K) sapphire immersion probes (HTSIPs) for use in ambient flames and gas turbine combustors. The development and evaluation of a fixed wavelength H2O absorption spectroscopy (FWAS) system that is demonstrates how the ECDL allows the system to operate in multiple modes that enhance FWAS measurement accuracy by improving wavelength position monitoring, and reducing non-absorption based contamination in spectral scans. The architecture of a high temperature (21000 K) and pressure (50 bar) database (HTPD) is developed that can enhance absorption spectroscopy based thermometry. The HTPD formation is developed by the evaluation of two approaches, a line-by-line (LBL) approach, where transition lineshape parameters are extracted from spectra and used along with a physics based model to allow the simulation of spectra over a wide range of temperatures and pressures, or an absorption cross-section (sigmaabs) approach, where spectra generated from a high temperature and pressure furnace are catalog spectra at various conditions forming a database of absorption cross-sections that is then interpolated to provide a simulated absorbance spectra based on measured reference grade spectra. Utilizing near future reference grade H2O absorption spectra, generated by the Sanders Group by means of an ECDL and a high temperature and pressure furnace, a unique opportunity is taken to provide the research community with a database that can be utilized for optical thermometry.

Full-potential theoretical investigations of electron inelastic mean free paths and extended x-ray absorption fine structure in molybdenum.

PubMed

Chantler, C T; Bourke, J D

2014-04-09

X-ray absorption fine structure (XAFS) spectroscopy is one of the most robust, adaptable, and widely used structural analysis tools available for a range of material classes from bulk solids to aqueous solutions and active catalytic structures. Recent developments in XAFS theory have enabled high-accuracy calculations of spectra over an extended energy range using full-potential cluster modelling, and have demonstrated particular sensitivity in XAFS to a fundamental electron transport property-the electron inelastic mean free path (IMFP). We develop electron IMFP theory using a unique hybrid model that simultaneously incorporates second-order excitation losses, while precisely accounting for optical transitions dictated by the complex band structure of the solid. These advances are coupled with improved XAFS modelling to determine wide energy-range absorption spectra for molybdenum. This represents a critical test case of the theory, as measurements of molybdenum K-edge XAFS represent the most accurate determinations of XAFS spectra for any material. We find that we are able to reproduce an extended range of oscillatory structure in the absorption spectrum, and demonstrate a first-time theoretical determination of the absorption coefficient of molybdenum over the entire extended XAFS range utilizing a full-potential cluster model.

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

PubMed

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

2015-03-07

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

Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

PubMed

Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

2017-05-09

An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2018-12-01

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

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. Copyright © 2015 Elsevier B.V. All rights reserved.

One-shot calculation of temperature-dependent optical spectra and phonon-induced band-gap renormalization

NASA Astrophysics Data System (ADS)

Zacharias, Marios; Giustino, Feliciano

2016-08-01

Recently, Zacharias et al. [Phys. Rev. Lett. 115, 177401 (2015), 10.1103/PhysRevLett.115.177401] developed an ab initio theory of temperature-dependent optical absorption spectra and band gaps in semiconductors and insulators. In that work, the zero-point renormalization and the temperature dependence were obtained by sampling the nuclear wave functions using a stochastic approach. In the present work, we show that the stochastic sampling of Zacharias et al. can be replaced by fully deterministic supercell calculations based on a single optimal configuration of the atomic positions. We demonstrate that a single calculation is able to capture the temperature-dependent band-gap renormalization including quantum nuclear effects in direct-gap and indirect-gap semiconductors, as well as phonon-assisted optical absorption in indirect-gap semiconductors. In order to demonstrate this methodology, we calculate from first principles the temperature-dependent optical absorption spectra and the renormalization of direct and indirect band gaps in silicon, diamond, and gallium arsenide, and we obtain good agreement with experiment and with previous calculations. In this work we also establish the formal connection between the Williams-Lax theory of optical transitions and the related theories of indirect absorption by Hall, Bardeen, and Blatt, and of temperature-dependent band structures by Allen and Heine. The present methodology enables systematic ab initio calculations of optical absorption spectra at finite temperature, including both direct and indirect transitions. This feature will be useful for high-throughput calculations of optical properties at finite temperature and for calculating temperature-dependent optical properties using high-level theories such as G W and Bethe-Salpeter approaches.

Spectral Changes of Erythrosin B Luminescence Upon Binding to Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Sablin, N. V.; Gerasimova, M. A.; Nemtseva, E. V.

2016-04-01

Changes in absorption, fluorescence, phosphorescence, and delayed fluorescence spectra of erythrosin B are studied in the presence of bovine serum albumin at room temperature. Spectral and chronoscopic characteristics of the observed photophysical processes are defined. The binding of erythrosin B with the protein followed by spectral changes is demonstrated. Absorption and fluorescence spectra of the dye in the bound state are described, the binding mechanism is analyzed. The binding parameters of the dye-protein complex are estimated.

Comparative NEXAFS study of the selected icefish hard tissues and hydroxyapatite

NASA Astrophysics Data System (ADS)

Petrova, O. V.; Nekipelov, S. V.; Sivkov, D. V.; Mingaleva, A. E.; Nikolaev, A.; Frank-Kamenetskaya, O. V.; Bazhenov, V. V.; Vyalikh, D. V.; Molodtsov, S. L.; Sivkov, V. N.; Ehrlich, H.

2017-11-01

The structure of native Champsocephalus gunnari icefish otoliths, scales, teeth, bones and pristine hydroxyapatite (HA) were examined using Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. NEXAFS Cls-absorption spectra of the selected icefish hard tissues indicate that otoliths contain anion [CO3]2-. NEXAFS P2p-spectra clearly indicate the absence of phosphorus atoms only within otoliths and scales samples. However, the icefish teeth and bones P2p-spectra demonstrate identical spectral feature typical for the HA. NEXAFS Ca2p-spectra of the icefish hard tissues studied also shows features, which are in good correspondence with HA spectra. Interestingly, there is a red shift ≈ 0.1 eV of the 2p1/2,3/2 → 3d transition energies in NEXAFS Ca2p-spectra of teethes and bones of the C. gunnari in comparison to HA.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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.

Titan solar occultation observations reveal transit spectra of a hazy world.

PubMed

Robinson, Tyler D; Maltagliati, Luca; Marley, Mark S; Fortney, Jonathan J

2014-06-24

High-altitude clouds and hazes are integral to understanding exoplanet observations, and are proposed to explain observed featureless transit spectra. However, it is difficult to make inferences from these data because of the need to disentangle effects of gas absorption from haze extinction. Here, we turn to the quintessential hazy world, Titan, to clarify how high-altitude hazes influence transit spectra. We use solar occultation observations of Titan's atmosphere from the Visual and Infrared Mapping Spectrometer aboard National Aeronautics and Space Administration's (NASA) Cassini spacecraft to generate transit spectra. Data span 0.88-5 μm at a resolution of 12-18 nm, with uncertainties typically smaller than 1%. Our approach exploits symmetry between occultations and transits, producing transit radius spectra that inherently include the effects of haze multiple scattering, refraction, and gas absorption. We use a simple model of haze extinction to explore how Titan's haze affects its transit spectrum. Our spectra show strong methane-absorption features, and weaker features due to other gases. Most importantly, the data demonstrate that high-altitude hazes can severely limit the atmospheric depths probed by transit spectra, bounding observations to pressures smaller than 0.1-10 mbar, depending on wavelength. Unlike the usual assumption made when modeling and interpreting transit observations of potentially hazy worlds, the slope set by haze in our spectra is not flat, and creates a variation in transit height whose magnitude is comparable to those from the strongest gaseous-absorption features. These findings have important consequences for interpreting future exoplanet observations, including those from NASA's James Webb Space Telescope.

Near-edge X-ray refraction fine structure microscopy

DOE PAGES

Farmand, Maryam; Celestre, Richard; Denes, Peter; ...

2017-02-06

We demonstrate a method for obtaining increased spatial resolution and specificity in nanoscale chemical composition maps through the use of full refractive reference spectra in soft x-ray spectro-microscopy. Using soft x-ray ptychography, we measure both the absorption and refraction of x-rays through pristine reference materials as a function of photon energy and use these reference spectra as the basis for decomposing spatially resolved spectra from a heterogeneous sample, thereby quantifying the composition at high resolution. While conventional instruments are limited to absorption contrast, our novel refraction based method takes advantage of the strongly energy dependent scattering cross-section and can seemore » nearly five-fold improved spatial resolution on resonance.« less

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

NASA Astrophysics Data System (ADS)

Bychto, Leszek; Maliński, Mirosław; Patryn, Aleksy; Tivanov, Mikhail; Gremenok, Valery

2018-05-01

This paper presents a new method for computations of the optical absorption coefficient spectra from the normalized photoacoustic amplitude spectra of thin semiconductor samples deposited on the optically transparent and thermally thick substrates. This method was tested on CuIn(Te0.7Se0.3)2 thin films. From the normalized photoacoustic amplitude spectra, the optical absorption coefficient spectra were computed with the new formula as also with the numerical iterative method. From these spectra, the value of the energy gap of the thin film material and the type of the optical transitions were determined. From the experimental optical transmission spectra, the optical absorption coefficient spectra were computed too, and compared with the optical absorption coefficient spectra obtained from photoacoustic spectra.

Gas-phase infrared spectroscopy for determination of double bond configuration of monounsaturated compounds.

PubMed

Attygalle, A B; Svatos, A; Wilcox, C; Voerman, S

1994-05-15

Gas-phase Fourier-transform infrared spectra allow unambiguous determination of the configuration of the double bonds of long-chain unsaturated compounds bearing RCH=CHR' type bonds. Although the infrared absorption at 970-967 cm-1 has been used previously for the identification of trans bonds, the absorption at 3028-3011 cm-1 is conventionally considered to be incapable of distinguishing cis and trans isomers. In this paper, we present a large number of gas-phase spectra of monounsaturated long-chain acetates which demonstrate that an absorption, highly characteristic for the cis configuration, occurs at 3013-3011 cm-1, while trans compounds fail to show any bands in this region. However, if a double bond is present at the C-2 or C-3 carbon atoms, this cis=CH stretch absorption shows a hypsochromic shift to 3029-3028 and 3018-3017 cm-1, respectively. Similarly, if a cis double bond is present at the penultimate carbon atom, this band appears at 3022-3021 cm-1. All the spectra of trans alkenyl acetates showed the expected C-H wag absorption at 968-964 cm-1. In addition, the spectra of (E)-2-alkenyl acetates show a unique three-peak "finger-print" pattern which allows the identification of the position and configuration of this bond. Furthermore, by synthesizing and obtaining spectra of appropriate deuteriated compounds, we have proved that the 3013-3011 cm-1 band is representative of the C-H stretching vibration of cis compounds of RCH=CHR' type.

Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

PubMed

Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

2011-08-23

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption. © 2011 American Chemical Society

Titan solar occultation observations reveal transit spectra of a hazy world

PubMed Central

Robinson, Tyler D.; Maltagliati, Luca; Marley, Mark S.; Fortney, Jonathan J.

2014-01-01

High-altitude clouds and hazes are integral to understanding exoplanet observations, and are proposed to explain observed featureless transit spectra. However, it is difficult to make inferences from these data because of the need to disentangle effects of gas absorption from haze extinction. Here, we turn to the quintessential hazy world, Titan, to clarify how high-altitude hazes influence transit spectra. We use solar occultation observations of Titan’s atmosphere from the Visual and Infrared Mapping Spectrometer aboard National Aeronautics and Space Administration’s (NASA) Cassini spacecraft to generate transit spectra. Data span 0.88–5 μm at a resolution of 12–18 nm, with uncertainties typically smaller than 1%. Our approach exploits symmetry between occultations and transits, producing transit radius spectra that inherently include the effects of haze multiple scattering, refraction, and gas absorption. We use a simple model of haze extinction to explore how Titan’s haze affects its transit spectrum. Our spectra show strong methane-absorption features, and weaker features due to other gases. Most importantly, the data demonstrate that high-altitude hazes can severely limit the atmospheric depths probed by transit spectra, bounding observations to pressures smaller than 0.1–10 mbar, depending on wavelength. Unlike the usual assumption made when modeling and interpreting transit observations of potentially hazy worlds, the slope set by haze in our spectra is not flat, and creates a variation in transit height whose magnitude is comparable to those from the strongest gaseous-absorption features. These findings have important consequences for interpreting future exoplanet observations, including those from NASA’s James Webb Space Telescope. PMID:24876272

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)

Determination of total x-ray absorption coefficient using non-resonant x-ray emission

PubMed Central

Achkar, A. J.; Regier, T. Z.; Monkman, E. J.; Shen, K. M.; Hawthorn, D. G.

2011-01-01

An alternative measure of x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has recently been developed that is both bulk sensitive and free of saturation effects. Here we show that the angle dependence of IPFY can provide a measure directly proportional to the total x-ray absorption coefficient, µ(E). In contrast, fluorescence yield (FY) and electron yield (EY) spectra are offset and/or distorted from µ(E) by an unknown and difficult to measure amount. Moreover, our measurement can determine µ(E) in absolute units with no free parameters by scaling to µ(E) at the non-resonant emission energy. We demonstrate this technique with measurements on NiO and NdGaO3. Determining µ(E) across edge-steps enables the use of XAS as a non-destructive measure of material composition. In NdGaO3, we also demonstrate the utility of IPFY for insulating samples, where neither EY or FY provide reliable spectra due to sample charging and self-absorption effects, respectively. PMID:22355697

Measurements of spectral parameters of water-vapour transitions near 1388 and 1345 nm for accurate simulation of high-pressure absorption spectra

NASA Astrophysics Data System (ADS)

Liu, Xiang; Jeffries, Jay B.; Hanson, Ronald K.

2007-05-01

Quantitative near-infrared absorption spectroscopy of water-vapour overtone and combination bands at high pressures is complicated by pressure broadening and shifting of individual lines and the blending of neighbouring transitions. An experimental and computational methodology is developed to determine accurate high-pressure absorption spectra. This case study investigates two water-vapour transitions, one near 1388 nm (7203.9 cm-1) and the other near 1345 nm (7435.6 cm-1), for potential two-line absorption measurements of temperature in the range of 400-1050 K with a pressure varying from 5-25 atm. The required quantitative spectroscopy data (line strength, collisional broadening, and pressure-induced frequency shift) of the target transitions and their neighbours (a total of four H2O vapour transitions near 1388 nm and six transitions near 1345 nm) are measured in neat H2O vapour, H2O-air and H2O-CO2 mixtures as a function of temperature (296-1000 K) at low pressures (<800 Torr). Precise values of the line strength S(T), pressure-broadening coefficients γair(T) and \\gamma _{CO_2 } (T), and pressure-shift coefficients δair(T) and \\delta _{CO_2 } (T) for the ten transitions were inferred from the measured spectra and compared with data from HITRAN 2004. A hybrid spectroscopic database was constructed by modifying HITRAN 2004 to incorporate these values for simulation of water-vapour-absorption spectra at high pressures. Simulations using this hybrid database are in good agreement with high pressure experiments and demonstrate that data collected at modest pressures can be used to simulate high-pressure absorption spectra.

Spectra of polarized thermal radiation in a cloudy atmosphere: Line-by-Line and Monte Carlo model for passive remote sensing of cirrus and polar clouds

NASA Astrophysics Data System (ADS)

Fomin, Boris; Falaleeva, Victoria

2016-07-01

A polarized high-resolution 1-D model has been presented for TIR (Thermal Infrared) remote sensing application. It is based on the original versions of MC (Monte Carlo) and LbL (Line-by-Line) algorithms, which have shown their effectiveness when modelling the thermal radiation atmospheric transfer, taking into account, the semi-transparent Ci-type and polar clouds scattering, as well as the direct consideration of the spectra of molecular absorption. This model may be useful in the planning of satellite experiments and in the validation of similar models, which use the "k-distribution" or other approximations, to account for gaseous absorption. The example simulations demonstrate that, the selective gas absorption does not only significantly affect the absorption and emission of radiation, but also, its polarization in the Ci-type clouds. As a result, the spectra of polarized radiation contain important information about the clouds, and а high-resolution polarized limb sounding in the TIR, seems to be a useful tool in obtaining information on cloud types and their vertical structures.

Notes on Experiments.

ERIC Educational Resources Information Center

Physics Education, 1983

1983-01-01

Discusses investigations of mirages with an astronomical telescope and a way of demonstrating three of the main features of laser/maser action. Also discusses several physics demonstrations using color television. These include thin-film interference effects, single-slit diffraction, emission/absorption spectra, "rings and brushes"…

Energy-gap reduction in heavily doped silicon: Causes and consequences

NASA Astrophysics Data System (ADS)

Pantelides, Sokrates T.; Selloni, Annabella; Car, Roberto

1985-02-01

The authors review briefly the existing theoretical treatments of the various effects that contribute to the reduction of the energy gap in heavily doped Si, namely electron-electron and electron-impurity interactions and the effect of disorder in the impurity distribution. They then turn to the longstanding question why energy-gap reductions extracted from three different types of experiments have persistently produced values with substantial discrepancies, making it impossible to compare with theoretical values. First, they demonstrate that a meaningful comparison between theory and experiment can indeed be made if theoretical calculations are carried out for actual quantities that experiments measure, e.g. luminescence spectra, as recently done by Selloni and Pantelides. Then, they demonstrate that, independent of any theoretical calculations, the optical absorption spectra are fully consistent with the luminescence spectra and that the discrepancies in the energy-gap reductions extracted from the two sets of spectra are caused entirely by the curve-fitting procedures used in analyzing optical-absorption data. Finally, they show explicitly that, as already believed by many authors, energy-gap reductions extracted from electrical measurements on transistors do not correspond to true gap reductions. They identify two corrections that must be added to the values extracted from the electrical data in order to arrive at the true gap reductions and show that the resulting values are in good overall agreement with luminescence and absorption data. They, therefore, demonstrate that the observed reduction in emitter injection efficiency in bipolar transistors is not strictly due to a gap reduction, as generally believed, but to three very different effects.

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

PubMed

Zhou, Wen-Yi; Li, Shan-Shan; Song, Jie-Yao; Jiang, Min; Jiang, Tian-Jia; Liu, Jin-Yun; Liu, Jin-Huai; Huang, Xing-Jiu

2018-04-03

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 μA cm -2 μM -1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO 2- x ) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO 2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

Determination of absorption coefficient of nanofluids with unknown refractive index from reflection and transmission spectra

NASA Astrophysics Data System (ADS)

Kim, Joong Bae; Lee, Seungyoon; Lee, Kyungeun; Lee, Ikjin; Lee, Bong Jae

2018-07-01

It has been shown that the absorption coefficient of a nanofluid can be actively tuned by changing material, size, shape, and concentration of the nanoparticle suspension. In applications of engineered nanofluids for the direct absorption of solar radiation, it is important to experimentally characterize the absorption coefficient of nanofluids in the solar spectrum. If the refractive index of the base fluid (i.e., the solution without nanoparticles) is known a priori, the absorption coefficient of nanofluids can be easily determined from the transmission spectrum. However, if the refractive index of the base fluid is not known, it is not straightforward to extract the absorption coefficient solely from the transmission spectrum. The present work aims to develop an analytical method of determining the absorption coefficient of nanofluids with unknown refractive index by measuring both reflection and transmission spectra. The proposed method will be validated with deionized water, and the effect of measurement uncertainty will be carefully examined. Finally, the general applicability of the proposed method will also be demonstrated for Therminol VP-1 as well as the Therminol VP-1 - graphite nanofluid.

Harnessing molecular excited states with Lanczos chains.

PubMed

Baroni, Stefano; Gebauer, Ralph; Bariş Malcioğlu, O; Saad, Yousef; Umari, Paolo; Xian, Jiawei

2010-02-24

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

Harnessing molecular excited states with Lanczos chains

NASA Astrophysics Data System (ADS)

Baroni, Stefano; Gebauer, Ralph; Bariş Malcioğlu, O.; Saad, Yousef; Umari, Paolo; Xian, Jiawei

2010-02-01

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

QCL spectroscopy combined with the least squares method for substance analysis

NASA Astrophysics Data System (ADS)

Samsonov, D. A.; Tabalina, A. S.; Fufurin, I. L.

2017-11-01

The article briefly describes distinctive features of quantum cascade lasers (QCL). It also describes an experimental set-up for acquiring mid-infrared absorption spectra using QCL. The paper demonstrates experimental results in the form of normed spectra. We tested the application of the least squares method for spectrum analysis. We used this method for substance identification and extraction of concentration data. We compare the results with more common methods of absorption spectroscopy. Eventually, we prove the feasibility of using this simple method for quantitative and qualitative analysis of experimental data acquired with QCL.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

NASA Astrophysics Data System (ADS)

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-04-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called ``molecular movie'' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

PubMed Central

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-01-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes. PMID:24740172

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

DOE PAGES

Gaudin, J.; Fourment, C.; Cho, B. I.; ...

2014-04-17

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level ofmore » the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.« less

Measurements of ionization states in warm dense aluminum with betatron radiation

NASA Astrophysics Data System (ADS)

Mo, M. Z.; Chen, Z.; Fourmaux, S.; Saraf, A.; Kerr, S.; Otani, K.; Masoud, R.; Kieffer, J.-C.; Tsui, Y.; Ng, A.; Fedosejevs, R.

2017-05-01

Time-resolved measurements of the ionization states of warm dense aluminum via K-shell absorption spectroscopy are demonstrated using betatron radiation generated from laser wakefield acceleration as a probe. The warm dense aluminum is generated by irradiating a free-standing nanofoil with a femtosecond optical laser pulse and was heated to an electron temperature of ˜20 -25 eV at a close-to-solid mass density. Absorption dips in the transmitted x-ray spectrum due to the Al4 + and Al5 + ions are clearly seen during the experiments. The measured absorption spectra are compared to simulations with various ionization potential depression models, including the commonly used Stewart-Pyatt model and an alternative modified Ecker-Kröll model. The observed absorption spectra are in approximate agreement with these models, though indicating a slightly higher state of ionization and closer agreement for simulations with the modified Ecker-Kröll model.

Heterodyne-detected dispersed vibrational echo spectroscopy.

PubMed

Jones, Kevin C; Ganim, Ziad; Tokmakoff, Andrei

2009-12-24

We develop heterodyned dispersed vibrational echo spectroscopy (HDVE) and demonstrate the new capabilities in biophysical applications. HDVE is a robust ultrafast technique that provides a characterization of the real and imaginary components of third-order nonlinear signals with high sensitivity and single-laser-shot capability and can be used to extract dispersed pump-probe and dispersed vibrational echo spectra. Four methods for acquiring HDVE phase and amplitude spectra were compared: Fourier transform spectral interferometry, a new phase modulation spectral interferometry technique, and combination schemes. These extraction techniques were demonstrated in the context of protein amide I spectroscopy. Experimental HDVE and heterodyned free induction decay amide I spectra were explicitly compared to conventional dispersed pump-probe, dispersed vibrational echo, and absorption spectra. The new capabilities of HDVE were demonstrated by acquiring single-shot spectra and melting curves of ubiquitin and concentration-dependent spectra of insulin suitable for extracting the binding constant for dimerization. The introduced techniques will prove particularly useful in transient experiments, studying irreversible reactions, and micromolar concentration studies of small proteins.

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

PubMed Central

2015-01-01

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

Synthesis, physical properties and self-assembly behavior of azole-fused pyrene derivatives

NASA Astrophysics Data System (ADS)

Xiao, Jinchong; Xiao, Xuyu; Zhao, Yanlei; Wu, Bo; Liu, Zhenying; Zhang, Xuemin; Wang, Sujuan; Zhao, Xiaohui; Liu, Lei; Jiang, Li

2013-05-01

A novel selenadiazole-fused pyrene derivative PySe was successfully synthesized and characterized. Its single structure is almost planar and adopts a sandwich-herringbone packing model. The self-assembly behaviors based on compound PySe and its analogue thiadiazole-fused pyrene derivative PyS were studied in detail and the as-formed nanostructures were fully characterized by means of UV-vis absorption, emission spectra, X-ray diffraction, field emission SEM and TEM. We attribute the bathochromic shift absorption and emission spectra of PyS and PySe in aqueous solution to the formation of J-type aggregation. In addition, our investigation demonstrated that the shape and size of the as-prepared nanostructures could be tuned by different chalcogen analogues and the volume ratio of water to organic solvent.A novel selenadiazole-fused pyrene derivative PySe was successfully synthesized and characterized. Its single structure is almost planar and adopts a sandwich-herringbone packing model. The self-assembly behaviors based on compound PySe and its analogue thiadiazole-fused pyrene derivative PyS were studied in detail and the as-formed nanostructures were fully characterized by means of UV-vis absorption, emission spectra, X-ray diffraction, field emission SEM and TEM. We attribute the bathochromic shift absorption and emission spectra of PyS and PySe in aqueous solution to the formation of J-type aggregation. In addition, our investigation demonstrated that the shape and size of the as-prepared nanostructures could be tuned by different chalcogen analogues and the volume ratio of water to organic solvent. Electronic supplementary information (ESI) available: TGA analysis, spectra characterization data for compound 1, 2, 3 and X-ray crystallographic data for compound PySe (2, CIF). CCDC 917821. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr00523b

Excitonic nature of optical transitions in electroabsorption spectra of perovskite solar cells

NASA Astrophysics Data System (ADS)

Ruf, Fabian; Magin, Alice; Schultes, Moritz; Ahlswede, Erik; Kalt, Heinz; Hetterich, Michael

2018-02-01

We investigate the electronic structure of solution-processed perovskite solar cells using temperature-dependent electroabsorption (EA) spectroscopy. Simultaneous measurements of absorption and electromodulated spectra of semitransparent methylammonium lead iodide solar cells facilitate a direct comparison of the specific features. The EA spectra can be transformed to peak-like line shapes utilizing an approach based on the Kramers-Kronig relations. The resulting peak positions correspond well to the discrete excitonic—rather than the continuum—contribution of the absorption spectra derived from generalized Elliott fits. This indicates the excitonic nature of the observed EA resonance and is found to be consistent over the whole temperature range investigated (from T = 10 K up to room temperature). To further confirm these findings, a line shape analysis of the measured EA spectra was performed. The best agreement was achieved using a first-derivative-like functional form which is expected for excitonic systems and supports the conclusion of an excitonic optical transition. Exciton binding energies EB are estimated for the orthorhombic and tetragonal phases as 26 meV and 19 meV, respectively. Nevertheless, power-conversion efficiencies η up to 13% (11.5% stabilized) demonstrate good charge-carrier separation in the devices due to sufficient thermal dissociation and Sommerfeld-enhanced absorption.

Instant detection and identification of concealed explosive-related compounds: Induced Stokes Raman versus infrared.

PubMed

Elbasuney, Sherif; El-Sherif, Ashraf F

2017-01-01

The instant detection of explosives and explosive-related compounds has become an urgent priority in recent years for homeland security and counter-terrorism applications. Modern techniques should offer enhancement in selectivity, sensitivity, and standoff distances. Miniaturisation, portability, and field-ruggedisation are crucial requirements. This study reports on instant and standoff identification of concealed explosive-related compounds using customized Raman technique. Stokes Raman spectra of common explosive-related compounds were generated and spectrally resolved to create characteristic finger print spectra. The scattered Raman emissions over the band 400:2000cm -1 were compared to infrared absorption using FTIR. It has been demonstrated that the two vibrational spectroscopic techniques were opposite and completing each other. Molecular vibrations with strong absorption in infrared (those involve strong change in dipole moments) induced weak signals in Raman and vice versa. The tailored Raman offered instant detection, high sensitivity, and standoff detection capabilities. Raman demonstrated characteristic fingerprint spectra with stable baseline and sharp intense peaks. Complete correlations of absorption/scattered signals to certain molecular vibrations were conducted to generate an entire spectroscopic profile of explosive-related compounds. This manuscript shades the light on Raman as one of the prevailing technologies for instantaneous detection of explosive-related compounds. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides

NASA Astrophysics Data System (ADS)

Suganya, Krishnasamy; Kabilan, Senthamaraikannan

2004-04-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Resolving Spectral Lines with a Periscope-Type DVD Spectroscope

ERIC Educational Resources Information Center

Wakabayashi, Fumitaka

2008-01-01

A new type of DVD spectroscope, the periscope type, is described and the numerical analysis of the observed emission and absorption spectra is demonstrated. A small and thin mirror is put inside and an eighth part of a DVD is used as a grating. Using this improved DVD spectroscope, one can observe and photograph visible spectra more easily and…

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2016-10-01

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

Real Time Diagnostics of Jet Engine Exhaust Plumes Using a Chirped QC Laser Spectrometer

NASA Astrophysics Data System (ADS)

Hay, K. G.; Duxbury, G.; Langford, N.

2010-06-01

Quantitative measurements of real-time variations of the chemical composition of a jet engine exhaust plume is demonstrated using a 4.86 μmn intra-pulse quantum cascade laser spectrometer. The measurements of the gas turbine exhaust were carried out in collaboration with John Black and Mark Johnson at Rolls Royce. The recording of five sets of averaged spectra a second has allowed us to follow the build up of the combustion products within the exhaust, and to demonstrate the large variation of the integrated absorption of these absorption lines with temperature. The absorption cross sections of the lines of both carbon monoxide and water increase with temperature, whereas those of the three main absorption lines of carbon dioxide decrease. At the steady state limit the absorption lines of carbon dioxide are barely visible, and the spectrum is dominated by absorption lines of carbon monoxide and water.

Synthesis and binding properties of arylethyne-linked porphyrin-zinc complexes for organic electronics applications.

PubMed

Reainthippayasakul, W; Paosawatyanyong, B; Bhanthumnavin, W

2013-05-01

Conjugated meso-alkynyl 5,15-dimesitylporphyrin metal complexes have been synthesized by Sonogashira coupling reaction in good yields. Alkynyl groups were chosen as a link at the meso positions in order to extend the pi-conjugated length of porphyrin rings. These synthesized porphyrin derivatives were characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Moreover, UV-visible spectroscopy and fluorescence spectroscopy were also used to investigate their photophysical properties. It has been demonstrated that central metal ions as well as meso substituents on porphyrin rings affected the electronic absorption and emission spectra of the compounds. Spectroscopic results revealed that alkyne-linked porphyrin metal complexes showed higher pi-conjugation compared with porphyrin building blocks resulting in red shifts in both absorption and emission spectra. Coordination properties of synthesized porphyrins were preliminarily investigated by UV-visible absorption and fluorescence emission spectroscopic titration with pyridine as axial ligand. The formation of porphyrin-pyridine complexes resulted in significant red shifts in absorption spectra and decrease of fluorescence intensity in emission spectra. Moreover, the 1H NMR titration experiments suggested that central metal ions play an important role to coordinate with pyridine and the coordination of porphyrin zinc(II) complex with pyridine occur in a 1:1 ratio. From these spectroscopic results, alkyne-linked porphyrin metal complexes offer potential applications as materials for optical organic nanosensors.

Infrared absorption nano-spectroscopy using sample photoexpansion induced by tunable quantum cascade lasers.

PubMed

Lu, Feng; Belkin, Mikhail A

2011-10-10

We report a simple technique that allows obtaining mid-infrared absorption spectra with nanoscale spatial resolution under low-power illumination from tunable quantum cascade lasers. Light absorption is detected by measuring associated sample thermal expansion with an atomic force microscope. To detect minute thermal expansion we tune the repetition frequency of laser pulses in resonance with the mechanical frequency of the atomic force microscope cantilever. Spatial resolution of better than 50 nm is experimentally demonstrated.

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 of plant phenolics and terpenes relative to dominant leaf biochemistry (water, chlorophyll, protein/nitrogen, cellulose, and lignin).

Ionic species produced on gamma radiolysis: Studies by matrix isolation technique—I. Electronic absorption spectra of perfluorosubstituted aromatic radical anions

NASA Astrophysics Data System (ADS)

Shou-te, Lian C. T.; Mittal, Jai P.

The absorption spectra of several perfluorosubstituted aromatic radical anions are compared with the corresponding perhydro compounds in which the various transitions involved have been assigned to those predicted theoretically. The electronic absorption spectra were obtained for pentafluorostyrene, pentafluorobenzaldehyde, pentafluorobenzoic acid, pentafluorobenzonitride, tetrafluorophthalic acid and pentafluoroaniline, by gamma radiolysis in 2-methyltetrahydrofuran at 77 K. A general similarity in the absorption spectra between the perfluorinated and the corresponding perhydro radical anion is observed except for a shift in the absorption band.

Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides.

PubMed

Suganya, Krishnasamy; Kabilan, Senthamaraikannan

2004-04-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed. Copyright 2003 Elsevier B.V.

Characterization of Lignin in Situ by Photoacoustic Spectroscopy

PubMed Central

Gould, J. Michael

1982-01-01

Photoacoustic spectroscopy is a recently developed nondestructive analytical technique that provides ultraviolet, visible, and infrared absorption spectra from intensely light scattering, solid, and/or optically opaque materials not suitable for conventional spectrophotometric analysis. In wood and other lignocellulosics, the principal ultraviolet absorption bands, in the absence of photosynthetic pigments, arise from the aromatic lignin component of the cell walls. Photoacoustic spectra of extracted lignin fragments (milled wood lignin) and synthetic lignin-like polymers contain a single major absorption band at 280 nanometers with an absorption tail extending beyond 400 nanometers. Photoacoustic spectra of pine, maple, and oak lignin in situ contain a broad primary absorption band at 300 nanometers and a longer wavelength shoulder around 370 nanometers. Wheat lignin in situ, on the other hand, exhibits two principle absorption peaks, at 280 nanometers and 320 nanometers. The presence of absorption bands at wavelengths greater than 300 nanometers in intact lignin could result from (a) interacting, nonconjugated chromophores, or (b) the presence of more highly conjugated structural components formed as the result of oxidation of the polymer. Evidence for the latter comes from the observation that, on the outer surface of senescent, field-dried wheat culms (stems), new absorption bands in the 350 to 400 nanometer region predominate. These new bands are less apparent on the outer surface of presenescent wheat culms and are virtually absent on the inner surface of either senescent or presenescent culms, suggesting that the appearance of longer wavelength absorption bands in senescent wheat is the result of accumulated photochemical modifications of the ligin polymer. These studies also demonstrate photoacoustic spectroscopy to be an important new tool for the investigation of insoluble plant components. PMID:16662709

Theoretical investigation on ratiometric two-photon fluorescent probe for Zn2+ detection based on ICT mechanism

NASA Astrophysics Data System (ADS)

Huang, Shuang; Yang, Bao-Zhu; Ren, Ai-Min

2016-06-01

OPA (one-photon absorption), TPA (two-photon absorption) and fluorescence properties of a free ligand L upon coordination with Zn2+, and the regeneration with CN- were investigated in theory. According to our research, OPA spectra of ligand L show red-shift binding with Zn2+ while blue-shift with CN-. The fluorescence spectra and TPA wavelength are shifted in the same situation as those of OPA spectra. The value of TPA cross-section decreased at first, and then increased to 1813 GM for [L-Zn(CN)4]2-. Intramolecular charge transfer (ICT) mechanism was investigated by natural bond orbital (NBO) analysis. It demonstrates that L is hopeful to be a good ratiometric fluorescent probe for zinc ion detection in solution, and it can regenerate after CN- was introduced.

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.

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.

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

NASA Technical Reports Server (NTRS)

Singhroy, Vernon H.; Kruse, Fred A.

1991-01-01

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

X-Ray Absorption Measured in the Resonant Auger Scattering Mode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hikosaka, Y.; Shigemasa, E.; Kaneyasu, T.

2008-08-15

We report both experimental and theoretical studies on x-ray absorption measured in the resonant Auger scattering mode of gas phase carbon monoxide near the O1s{yields}2{pi} region. Both experiment and theory display a crucial difference between the x-ray absorption profiles obtained in the conventional and resonant scattering modes. Lifetime vibrational interference is the main source of the difference. It is demonstrated that such interference, which arises from a coherent excitation to overlapping intermediate levels, ruins the idea for obtaining x-ray absorption spectra in a lifetime broadening free regime.

Numerical simulation of infrared radiation absorption for diagnostics of gas-aerosol medium by remote sensing data

NASA Astrophysics Data System (ADS)

Voitsekhovskaya, O. K.; Egorov, O. V.; Kashirskii, D. E.; Shefer, O. V.

2015-11-01

Calculated absorption spectra of the mixture of gases (H2O, CO, CO2, NO, NO2, and SO2) and aerosol (soot and Al2O3), contained in the exhausts of aircraft and rocket engines are demonstrated. Based on the model of gas-aerosol medium, a numerical study of the spectral dependence of the absorptance for different ratios of gas and aerosol components was carried out. The influence of microphysical and optical properties of the components of the mixture on the spectral features of absorption of gas-aerosol medium was established.

Importance of the green color, absorption gradient, and spectral absorption of chloroplasts for the radiative energy balance of leaves.

PubMed

Kume, Atsushi

2017-05-01

Terrestrial green plants absorb photosynthetically active radiation (PAR; 400-700 nm) but do not absorb photons evenly across the PAR waveband. The spectral absorbance of photosystems and chloroplasts is lowest for green light, which occurs within the highest irradiance waveband of direct solar radiation. We demonstrate a close relationship between this phenomenon and the safe and efficient utilization of direct solar radiation in simple biophysiological models. The effects of spectral absorptance on the photon and irradiance absorption processes are evaluated using the spectra of direct and diffuse solar radiation. The radiation absorption of a leaf arises as a consequence of the absorption of chloroplasts. The photon absorption of chloroplasts is strongly dependent on the distribution of pigment concentrations and their absorbance spectra. While chloroplast movements in response to light are important mechanisms controlling PAR absorption, they are not effective for green light because chloroplasts have the lowest spectral absorptance in the waveband. With the development of palisade tissue, the incident photons per total palisade cell surface area and the absorbed photons per chloroplast decrease. The spectral absorbance of carotenoids is effective in eliminating shortwave PAR (<520 nm), which contains much of the surplus energy that is not used for photosynthesis and is dissipated as heat. The PAR absorptance of a whole leaf shows no substantial difference based on the spectra of direct or diffuse solar radiation. However, most of the near infrared radiation is unabsorbed and heat stress is greatly reduced. The incident solar radiation is too strong to be utilized for photosynthesis under the current CO 2 concentration in the terrestrial environment. Therefore, the photon absorption of a whole leaf is efficiently regulated by photosynthetic pigments with low spectral absorptance in the highest irradiance waveband and through a combination of pigment density distribution and leaf anatomical structures.

One-shot calculation of temperature-dependent optical spectra and phonon-induced band-gap renormalization

NASA Astrophysics Data System (ADS)

Zacharias, Marios; Giustino, Feliciano

Electron-phonon interactions are of fundamental importance in the study of the optical properties of solids at finite temperatures. Here we present a new first-principles computational technique based on the Williams-Lax theory for performing predictive calculations of the optical spectra, including quantum zero-point renormalization and indirect absorption. The calculation of the Williams-Lax optical spectra is computationally challenging, as it involves the sampling over all possible nuclear quantum states. We develop an efficient computational strategy for performing ''one-shot'' finite-temperature calculations. These require only a single optimal configuration of the atomic positions. We demonstrate our methodology for the case of Si, C, and GaAs, yielding absorption coefficients in good agreement with experiment. This work opens the way for systematic calculations of optical spectra at finite temperature. This work was supported by the UK EPSRC (EP/J009857/1 and EP/M020517/) and the Leverhulme Trust (RL-2012-001), and the Graphene Flagship (EU-FP7-604391).

Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, ChuanXiang; Zhao, Yi, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn; Liang, WanZhen, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn

2015-10-21

The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra withmore » respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.« less

Measurements of ionization states in warm dense aluminum with betatron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, M. Z.; Chen, Z.; Fourmaux, S.

Time-resolved measurements of the ionization states of warm dense aluminum via K-shell absorption spectroscopy are demonstrated using betatron radiation generated from laser wakefield acceleration as a probe. The warm dense aluminum is generated by irradiating a free-standing nanofoil with a femtosecond optical laser pulse and was heated to an electron temperature of ~20–25 eV at a close-to-solid mass density. Absorption dips in the transmitted x-ray spectrum due to the Al 4+ and Al 5+ ions are clearly seen during the experiments. The measured absorption spectra are compared to simulations with various ionization potential depression models, including the commonly used Stewart-Pyattmore » model and an alternative modified Ecker-Kröll model. Furthermore, the observed absorption spectra are in approximate agreement with these models, though indicating a slightly higher state of ionization and closer agreement for simulations with the modified Ecker-Kröll model.« less

A new high selective and sensitive turn-on fluorescent and ratiometric absorption chemosensor for Cu2+ based on benzimidazole in aqueous solution and its application in live cell.

PubMed

Bing, Qijing; Wang, Lin; Li, Donglin; Wang, Guang

2018-09-05

A new benzimidazole base turn-on fluorescent and ratiometric absorption chemosensor (L) bearing bidentate ligand for detection of Cu 2+ was designed and synthesized. Fluorescence and UV-vis spectra studies demonstrated that L can detect Cu 2+ ions in aqueous solution using fluorescence enhancement and ratiometric absorption sensing over a wide pH range. Both fluorescent and ratiometric absorption sensing of L for Cu 2+ possessed high selectivity and sensitivity over other competitive metal ions and had low detection limit. Job's plot, mass spectra and DFT calculation indicated the sensing mechanism is the complex formation between L and Cu 2+ with 1:2 stoichiometry. Fluorescence images of HepG2 in the absence and presence of Cu 2+ displayed L had cell permeability and detection ability for Cu 2+ in live cells. Copyright © 2018 Elsevier B.V. All rights reserved.

Measurements of ionization states in warm dense aluminum with betatron radiation

DOE PAGES

Mo, M. Z.; Chen, Z.; Fourmaux, S.; ...

2017-05-19

Time-resolved measurements of the ionization states of warm dense aluminum via K-shell absorption spectroscopy are demonstrated using betatron radiation generated from laser wakefield acceleration as a probe. The warm dense aluminum is generated by irradiating a free-standing nanofoil with a femtosecond optical laser pulse and was heated to an electron temperature of ~20–25 eV at a close-to-solid mass density. Absorption dips in the transmitted x-ray spectrum due to the Al 4+ and Al 5+ ions are clearly seen during the experiments. The measured absorption spectra are compared to simulations with various ionization potential depression models, including the commonly used Stewart-Pyattmore » model and an alternative modified Ecker-Kröll model. Furthermore, the observed absorption spectra are in approximate agreement with these models, though indicating a slightly higher state of ionization and closer agreement for simulations with the modified Ecker-Kröll model.« less

First Time Rapid and Accurate Detection of Massive Number of Metal Absorption Lines in the Early Universe Using Deep Neural Network

NASA Astrophysics Data System (ADS)

Zhao, Yinan; Ge, Jian; Yuan, Xiaoyong; Li, Xiaolin; Zhao, Tiffany; Wang, Cindy

2018-01-01

Metal absorption line systems in the distant quasar spectra have been used as one of the most powerful tools to probe gas content in the early Universe. The MgII λλ 2796, 2803 doublet is one of the most popular metal absorption lines and has been used to trace gas and global star formation at redshifts between ~0.5 to 2.5. In the past, machine learning algorithms have been used to detect absorption lines systems in the large sky survey, such as Principle Component Analysis, Gaussian Process and decision tree, but the overall detection process is not only complicated, but also time consuming. It usually takes a few months to go through the entire quasar spectral dataset from each of the Sloan Digital Sky Survey (SDSS) data release. In this work, we applied the deep neural network, or “ deep learning” algorithms, in the most recently SDSS DR14 quasar spectra and were able to randomly search 20000 quasar spectra and detect 2887 strong Mg II absorption features in just 9 seconds. Our detection algorithms were verified with previously released DR12 and DR7 data and published Mg II catalog and the detection accuracy is 90%. This is the first time that deep neural network has demonstrated its promising power in both speed and accuracy in replacing tedious, repetitive human work in searching for narrow absorption patterns in a big dataset. We will present our detection algorithms and also statistical results of the newly detected Mg II absorption lines.

Assessment of spectroscopic parameters of solvated Eu(dmh)3 phen organometallic complex in various basic and acidic solvents.

PubMed

Chitnis, Dipti; Kalyani, N Thejo; Dhoble, Sanjay

2018-05-31

We report on the comprehension of novel europium activated hybrid organic Eu(dmh) 3 phen (Eu: europium, dmh: 2,6-dimethyl-3,5-heptanedione, phen: 1,10 phenanthroline) organo-metallic complexes, synthesized at different pH values by the solution technique. Photo physical properties of these complexes in various basic and acidic solvents were probed by UV-vis optical absorption and photoluminescence (PL) spectra. Minute differences in optical absorption peaks with variable optical densities were encountered with the variation in solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid) media, revealing bathochromic shift in the absorption peaks. The PL spectra of the complex in various acidic and basic organic solvents revealed the position of the emission peak at 613 nm irrespective of the changes in solvents whereas the excitation spectrum almost matched with that of the UV-vis absorption data. The optical density was found to be maximum for the complex with pH 7.0 whereas it gradually decreased when pH was lowered to 6.0 or raised to 8.0 at an interval of 0.5, demonstrating its pH sensitive nature. Several spectroscopic parameters related to probability of transition such as absorbance A(λ), Napierian absorption coefficient α(λ), molecular absorption cross-section σ(λ), radiative lifetime (τ 0 ) and oscillator strength (f) were calculated from UV-vis spectra. The relative intensity ratio (R-ratio), calculated from the emission spectra was found to be almost the same in all the organic solvents. The optical energy gap, calculated for the designed complexes were found to be well in accordance with the ideal acceptance value of energy gap of the emissive materials used for fabrication of red organic light-emitting diode (OLED). The relation between Stoke's shift and solvent polarity function was established by Lippert-Mataga plot. This remarkable independence of the electronic absorption spectra of Eu complexes on the nature of the solvent with unique emission wavelength furnishes its potential to serve as a red light emitter for solution processed OLEDs, display panels and solid-state lighting. Copyright © 2018 John Wiley & Sons, Ltd.

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids.

PubMed

Shanthi, M; Kabilan, S

2007-06-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids

NASA Astrophysics Data System (ADS)

Shanthi, M.; Kabilan, S.

2007-06-01

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

A simple measurement method of molecular relaxation in a gas by reconstructing acoustic velocity dispersion

NASA Astrophysics Data System (ADS)

Zhu, Ming; Liu, Tingting; Zhang, Xiangqun; Li, Caiyun

2018-01-01

Recently, a decomposition method of acoustic relaxation absorption spectra was used to capture the entire molecular multimode relaxation process of gas. In this method, the acoustic attenuation and phase velocity were measured jointly based on the relaxation absorption spectra. However, fast and accurate measurements of the acoustic attenuation remain challenging. In this paper, we present a method of capturing the molecular relaxation process by only measuring acoustic velocity, without the necessity of obtaining acoustic absorption. The method is based on the fact that the frequency-dependent velocity dispersion of a multi-relaxation process in a gas is the serial connection of the dispersions of interior single-relaxation processes. Thus, one can capture the relaxation times and relaxation strengths of N decomposed single-relaxation dispersions to reconstruct the entire multi-relaxation dispersion using the measurements of acoustic velocity at 2N  +  1 frequencies. The reconstructed dispersion spectra are in good agreement with experimental data for various gases and mixtures. The simulations also demonstrate the robustness of our reconstructive method.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

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 rheniummore » 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.« less

The effect of viewing angle on the spectral behavior of a Gd plasma source near 6.7 nm

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Gorman, Colm; Li Bowen; Cummins, Thomas

2012-04-02

We have demonstrated the effect of viewing angle on the extreme ultraviolet (EUV) emission spectra of gadolinium (Gd) near 6.7 nm. The spectra are shown to have a strong dependence on viewing angle when produced with a laser pulse duration of 10 ns, which may be attributed to absorption by low ion stages of Gd and an angular variation in the ion distribution. Absorption effects are less pronounced at a 150-ps pulse duration due to reduced opacity resulting from plasma expansion. Thus for evaluating source intensity, it is necessary to allow for variation with both viewing angle and target orientation.

Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers

NASA Technical Reports Server (NTRS)

Scott, G. W.

1982-01-01

Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.

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.

A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest

NASA Astrophysics Data System (ADS)

Dahlberg, Peter D.; Boughter, Christopher T.; Faruk, Nabil F.; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A.; Shaiber, Alon; Sherani, Aiman; Zhang, Jiacheng; Jureller, Justin E.; Hammond, Adam T.

2016-11-01

A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH3NH3PbBr3 perovskites and measure differences between nanocrystal films and micron scale crystals.

A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest.

PubMed

Dahlberg, Peter D; Boughter, Christopher T; Faruk, Nabil F; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A; Shaiber, Alon; Sherani, Aiman; Zhang, Jiacheng; Jureller, Justin E; Hammond, Adam T

2016-11-01

A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH 3 NH 3 PbBr 3 perovskites and measure differences between nanocrystal films and micron scale crystals.

Raman spectra and optical trapping of highly refractive and nontransparent particles

NASA Astrophysics Data System (ADS)

Xie, Changan; Li, Yong-qing

2002-08-01

We measured the Raman spectra of single optically trapped highly refractive and nontransparent microscopic particles suspended in a liquid using an inverted confocal laser-tweezers-Raman-spectroscopy system. A low-power diode-laser beam of TEM00 mode was used both for optical trapping and Raman excitation of refractive, absorptive, and reflective metal particles. To form a stable trap for a nontransparent particle, the beam focus was located near the top of the particle and the particle was pushed against a glass plate by the axial repulsive force. Raman spectra from single micron-sized crystals with high index of refraction including silicon, germanium, and KNbO3, and from absorptive particles of black and color paints were recorded. Surface-enhanced Raman scattering of R6G and phenylalanine molecules absorbed on the surface of a trapped cluster of silver particles was also demonstrated.

Simultaneous optimization method for absorption spectroscopy postprocessing.

PubMed

Simms, Jean M; An, Xinliang; Brittelle, Mack S; Ramesh, Varun; Ghandhi, Jaal B; Sanders, Scott T

2015-05-10

A simultaneous optimization method is proposed for absorption spectroscopy postprocessing. This method is particularly useful for thermometry measurements based on congested spectra, as commonly encountered in combustion applications of H2O absorption spectroscopy. A comparison test demonstrated that the simultaneous optimization method had greater accuracy, greater precision, and was more user-independent than the common step-wise postprocessing method previously used by the authors. The simultaneous optimization method was also used to process experimental data from an environmental chamber and a constant volume combustion chamber, producing results with errors on the order of only 1%.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantouvalou, I., E-mail: ioanna.mantouvalou@tu-berlin.de; Witte, K.; Martyanov, W.

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

UV-Vis absorption spectra and electronic structure of merocyanines in the gas phase

NASA Astrophysics Data System (ADS)

Ishchenko, Alexander A.; Kulinich, Andrii V.; Bondarev, Stanislav L.; Raichenok, Tamara F.

2018-02-01

Gas-phase absorption spectra of a merocyanine vinylogous series have been studied for the first time. In vapour, their long-wavelength absorption bands were found to be considerably shifted hypsochromically, broader, more symmetrical, less intense, and their vinylene shift much smaller than even in low-polarity n-hexane. This indicates that in the gas phase their electronic structure closely approaches the nonpolar polyene limiting structure. The TDDFT calculations of the long-wavelength electronic transitions in the studied merocyanines in vacuo demonstrated good-to-excellent correlation - depending on the functional used - with the obtained experimental data. For comparison, the solvent effects was accounted for using the polarizable continuum model (PCM) with n-hexane and ethanol as low-polarity and high-polarity media, and compared with the UV-Vis spectral data in these solvents. In this case, the discrepancy between theory and experiment was much greater, increasing at that with the polymethine chain length.

Fast Time-Dependent Density Functional Theory Calculations of the X-ray Absorption Spectroscopy of Large Systems.

PubMed

Besley, Nicholas A

2016-10-11

The computational cost of calculations of K-edge X-ray absorption spectra using time-dependent density functional (TDDFT) within the Tamm-Dancoff approximation is significantly reduced through the introduction of a severe integral screening procedure that includes only integrals that involve the core s basis function of the absorbing atom(s) coupled with a reduced quality numerical quadrature for integrals associated with the exchange and correlation functionals. The memory required for the calculations is reduced through construction of the TDDFT matrix within the absorbing core orbitals excitation space and exploiting further truncation of the virtual orbital space. The resulting method, denoted fTDDFTs, leads to much faster calculations and makes the study of large systems tractable. The capability of the method is demonstrated through calculations of the X-ray absorption spectra at the carbon K-edge of chlorophyll a, C 60 and C 70 .

Dependence of the electronic absorption spectra of aqueous solutions of iodine monochloride on the conditions of dilution and storage time

NASA Astrophysics Data System (ADS)

Klyubin, V. V.; Klyubina, K. A.; Makovetskaya, K. N.

2017-04-01

The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl- are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (pH ≥ 12).

SU-F-J-46: Feasibility of Cerenkov Emission for Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oraiqat, I; Rehemtulla, A; Lam, K

2016-06-15

Purpose: Cerenkov emission (CE) is a promising tool for online tumor microenvironment interrogation and targeting during radiotherapy. In this work, we utilize CE generated during radiotherapy as a broadband excitation source for real-time absorption spectroscopy. We demonstrate the feasibility of CE spectroscopy using a controlled experiment of materials with known emission/absorption properties. Methods: A water tank is irradiated with 20 MeV electron beam to induce Cerenkov emission. Food coloring dyes (Yellow #5, Red #40, and Blue #1), which have known emission/absorption properties were added to the water tank with increasing concentration (1 drop (0.05 mL), 2 drops, and 4 dropsmore » from a dispenser bottle). The signal is collected using a condensing lens which is coupled into a 20m optical fiber that is fed into a spectrometer that measures the emitted spectra. The resulting spectra from water/food coloring dye solutions were normalized by the reference spectrum, which is the Cerenkov spectrum of pure water, correcting for both the nonlinearity of the broadband Cerenkov emission spectrum as well as the non-uniform spectral response of the spectrometer. The emitted spectra were then converted into absorbance and their characteristics were analyzed. Results: The food coloring dye had a drastic change on the Cerenkov emission, shifting its wavelength according to its visible color. The collected spectra showed various absorbance peaks which agrees with tabulated peak positions of the dyes added within 0.3% for yellow, 1.7% for red, and 0.16% for blue. The CE peak heights proportionally increased as the dye concentration is increased. Conclusion: This work shows the potential for real-time functional spectroscopy using Cerenkov emission during radiotherapy. It was demonstrated that molecule identification as well as relative concentration can be extracted from the Cerenkov emission color shift.« less

Unveiling the Diffuse, Neutral Interstellar Medium: Absorption Spectroscopy of Galactic Hydrogen

NASA Astrophysics Data System (ADS)

Murray, Claire Elizabeth

The formation of stars and evolution of galaxies depends on the cycle of interstellar matter between supernova-expelled plasma and molecule-rich gas. At the center of this cycle is multiphase neutral hydrogen (HI), whose physical conditions provide key ingredients to theoretical models. However, constraints for HI properties require measurements of gas emission and absorption which have been severely limited by previous observational capabilities. In this thesis, I present the largest survey of Galactic HI absorption ever undertaken with the Karl G. Jansky Very Large Array (VLA). The survey, 21 cm Spectral Line Observations of Neutral Gas with the VLA (21-SPONGE), is a statistical study of HI in all phases using direct absorption measurements. Leveraging novel calibration techniques, I demonstrate the capability of the VLA to detect a significant sample of 21 cm absorption lines from warm, diffuse HI. To maximize observational sensitivity, I stack the 21-SPONGE spectra and detect a pervasive signature of the warm neutral medium in absorption. The inferred excitation (or spin) temperature is consistent with existing estimates, yet higher than predictions from theoretical models of collisional HI excitation. This suggests that radiative feedback via resonant scattering of Lyalpha photons, known as the Wouthuysen-Field effect, is influential with important implications for cosmological 21 cm observations. Next, I compare 21-SPONGE with synthetic HI spectra from 3D numerical simulations using a new, objective decomposition and radiative transfer tool. I quantify the recovery of HI structures and their properties by Gaussian-fitted 21 cm spectral lines for the first time. I find that 21 cm absorption line shapes are sensitive to simulated physics, and demonstrate that my analysis method is a powerful tool for diagnosing neutral ISM conditions. Finally, I compare properties inferred from synthetic spectra with "true" simulation results to construct a bias correction function for estimating HI properties. I apply this correction to the mass distribution of HI as a function of temperature from 21-SPONGE, and find a significant fraction of thermally unstable gas. This confirms that non-steady radiative and dynamical processes, such as turbulence and supernovae, have a strong influence on the thermodynamic state of the ISM.

High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xin

1996-12-01

X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

First-principles C band absorption spectra of SO2 and its isotopologues

NASA Astrophysics Data System (ADS)

Jiang, Bin; Kumar, Praveen; Kłos, Jacek; Alexander, Millard H.; Poirier, Bill; Guo, Hua

2017-04-01

The low-energy wing of the C ˜ B12 ←X˜ 1A1 absorption spectra for SO2 in the ultraviolet region is computed for the 32S,33S,34S and 36S isotopes, using the recently developed ab initio potential energy surfaces (PESs) of the two electronic states and the corresponding transition dipole surface. The state-resolved absorption spectra from various ro-vibrational states of SO2(X˜ 1A1 ) are computed. When contributions of these excited ro-vibrational states are included, the thermally averaged spectra are broadened but maintain their key characters. Excellent agreement with experimental absorption spectra is found, validating the accuracy of the PESs. The isotope shifts of the absorption peaks are found to increase linearly with energy, in good agreement with experiment.

On the nature of solvatochromic effect: The riboflavin absorption spectrum as a case study

NASA Astrophysics Data System (ADS)

Daidone, Isabella; Amadei, Andrea; Aschi, Massimiliano; Zanetti-Polzi, Laura

2018-03-01

We present here the calculation of the absorption spectrum of riboflavin in acetonitrile and dimethyl sulfoxide using a hybrid quantum/classical approach, namely the perturbed matrix method, based on quantum mechanical calculations and molecular dynamics simulations. The calculated spectra are compared to the absorption spectrum of riboflavin previously calculated in water and to the experimental spectra obtained in all three solvents. The experimentally observed variations in the absorption spectra upon change of the solvent environment are well reproduced by the calculated spectra. In addition, the nature of the excited states of riboflavin interacting with different solvents is investigated, showing that environment effects determine a recombination of the gas-phase electronic states and that such a recombination is strongly affected by the polarity of the solvent inducing significant changes in the absorption spectra.

On the possibility of real time air quality and toxicology assessment using multi-wavelength photoacoustic spectroscopy

NASA Astrophysics Data System (ADS)

Ajtai, Tibor; Pinter, Mate; Utry, Noemi; Kiss-Albert, Gergely; Palagyi, Andrea; Manczinger, Laszlo; Vagvölgyi, Csaba; Szabo, Gabor; Bozoki, Zoltan

2016-04-01

In this study we present results of field measurement campaigns focusing on the in-situ characterization of absorption spectra and the health relevance of light absorbing carbonaceous (LAC) in the ambient. The absorption spectra is measured @ 266, 355, 532 and 1064 nm by our state-of-the-art four-wavelength photoacoustic instrument, while for health relevance the eco- cito and genotoxicity parameters were measured using standardized methodologies. We experimentally demonstrated a correlation between the toxicities and the measured absorption spectra quantified by its wavelength dependency. Based on this correlation, we present novel possibilities on real-time air quality monitoring. LAC is extensively studied not only because of its considerable climate effects but as a serious air pollutant too. Gradually increasing number of studies demonstrated experimentally that the health effect of LAC is more serious than it is expected based on its share in total atmospheric aerosol mass. Furthermore during many local pollution events LAC not only has dominancy but it is close to exclusivity. Altogether due to its climate and health effects many studies and proposed regulations focus on the physical, chemical and toxicological properties of LAC as well as on its source apportionment. Despites of its importance, there is not yet a widely accepted standard methodology for the real-time and selective identification of LAC. There are many different reasons of that: starting from its complex inherent physicochemical features including many unknown constituents, via masking effect of ambient on the inherent physicochemical properties taking place even in case of a short residence, ending with the lack of reliable instrumentation for its health or source relevant parameters. Therefore, the methodology and instrument development for selective and reliable identification of LAC is timely and important issues in climate and air quality researches. Recently, many studies demonstrated correlation between the chemical compositions and the absorption features of LAC which open up novel possibilities in real time source apportionment and in air quality monitoring.

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 spectral influences of plant phenolics and terpenes relative to dominant leaf biochemistry (water, chlorophyll, protein/nitrogen, cellulose, and lignin).

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

PubMed Central

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A.

2016-01-01

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe3O4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level. PMID:27930297

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

DOE PAGES

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; ...

2016-12-07

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathwaymore » of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. Lastly, these results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.« less

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography.

PubMed

Zhu, Xiaohui; Hitchcock, Adam P; Bazylinski, Dennis A; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A

2016-12-20

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3 O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.

Temperature effects on quasi-isolated conjugated polymers as revealed by temperature-dependent optical spectra of 16-mer oligothiophene diluted in a sold matrix.

PubMed

Kanemoto, Katsuichi; Akai, Ichiro; Sugisaki, Mitsuru; Hashimoto, Hideki; Karasawa, Tsutomu; Negishi, Nobukazu; Aso, Yoshio

2009-06-21

Temperature dependences (4-300 K) of photoluminescence (PL) and absorption spectra of 16-mer oligothiophene (16 T) extremely diluted in polypropylene (PP) have been investigated in order to clarify temperature effects on quasi-isolated conjugated polymers. The PL and absorption spectra are found to blueshift with increasing temperature. The reason for the blueshift is discussed by comparing models based on the refractive index of the solvent (PP) and on the thermal conformational change of 16 T. The blueshift is concluded to result from the thermal conformational change. Time-resolved PL spectra show a redshift of PL band following photoexcitation (spectral migration). The amount of the migration is shown to increase with increasing temperature. The increased migration is concluded to be due to the thermal conformational change. The temperature dependence of the effective conjugation length (ECL) of 16 T is calculated for the absorption and PL transitions. The calculation suggests that ECL is reduced at room temperature to two-thirds of the intrinsic chain length. The activation energy of the conformational change is estimated to be 22.4 meV from the temperature dependence of ECL. We demonstrate that the steady-state PL spectra are well reproduced by simple Franck-Condon analyses using a single Huang-Ryes factor over a wide temperature range. The analyses reveal features of temperature dependence in important spectral parameters such as the Stokes shift, linewidth, and Huang-Ryes factor.

Mathematical modeling of reflectance and intrinsic fluorescence for cancer detection in human pancreatic tissue

NASA Astrophysics Data System (ADS)

Wilson, Robert H.; Chandra, Malavika; Scheiman, James; Simeone, Diane; McKenna, Barbara; Purdy, Julianne; Mycek, Mary-Ann

2009-02-01

Pancreatic adenocarcinoma has a five-year survival rate of only 4%, largely because an effective procedure for early detection has not been developed. In this study, mathematical modeling of reflectance and fluorescence spectra was utilized to quantitatively characterize differences between normal pancreatic tissue, pancreatitis, and pancreatic adenocarcinoma. Initial attempts at separating the spectra of different tissue types involved dividing fluorescence by reflectance, and removing absorption artifacts by applying a "reverse Beer-Lambert factor" when the absorption coefficient was modeled as a linear combination of the extinction coefficients of oxy- and deoxy-hemoglobin. These procedures demonstrated the need for a more complete mathematical model to quantitatively describe fluorescence and reflectance for minimally-invasive fiber-based optical diagnostics in the pancreas.

LASER METHODS IN MEDICINE: Light absorption in blood during low-intensity laser irradiation of skin

NASA Astrophysics Data System (ADS)

Barun, V. V.; Ivanov, A. P.

2010-06-01

An analytical procedure is proposed for describing optical fields in biological tissues inhomogeneous in the depth direction, such as human skin, with allowance for multiple scattering. The procedure is used to investigate the depth distribution of the optical power density in homogeneous and multilayer dermis when the skin is exposed to a laser beam. We calculate the absorbed laser power spectra for oxy- and deoxyhaemoglobin at different depths in relation to the absorption selectivity of these haemoglobin derivatives and the spectral dependence of the optical power density and demonstrate that the spectra vary considerably with depth. A simple exponential approximation is proposed for the depth distribution of the power density in the epidermis and dermis.

Determination of morphological characteristics of metallic nanoparticles based on modified Maxwell-Garnett fitting of optical responses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Battie, Y., E-mail: yann.battie@univ-lorraine.fr; Resano-Garcia, A.; En Naciri, A.

2015-10-05

A modified effective medium theory (MEMT) is introduced to determine morphological characteristics and the volume fraction of colloidal metallic nanoparticles. By analyzing the optical absorption spectra of gold nanoparticles (NPs), this model is used to determine the distribution of prolate and oblate NPs and to demonstrate the presence of spherical NPs. In addition to interband transition, the model takes into account the longitudinal and transversal surface plasmon resonances. The results predicted by the MEMT theory were found to be in very good agreement with the shape distributions obtained by transmission electron microscopy. We found that fitting optical absorption spectra usingmore » MEMT provides a robust tool for measuring the shape and concentration of metallic NPs.« less

Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

NASA Astrophysics Data System (ADS)

Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

2005-11-01

Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

Reflectance spectroscopy (0.35-8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

NASA Astrophysics Data System (ADS)

Berg, Breanne L.; Cloutis, Edward A.; Beck, Pierre; Vernazza, Pierre; Bishop, Janice L.; Takir, Driss; Reddy, Vishnu; Applin, Daniel; Mann, Paul

2016-02-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35-8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

Reflectance spectroscopy (0.35–8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

USGS Publications Warehouse

Berg, Breanne L.; Cloutis, Edward A.; Beck, P.; Vernazza, P.; Bishop, Janice L; Takir, Driss; Reddy, V.; Applin, D.; Mann, Paul

2016-01-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35–8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

Vibrationally high-resolved electronic spectra of MCl2 (M=C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2(.).

PubMed

Ran, Yibin; Pang, Min; Shen, Wei; Li, Ming; He, Rongxing

2016-10-05

We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M=C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group. Copyright © 2016 Elsevier B.V. All rights reserved.

Calibration-free sensor for pressure and H2O concentration in headspace of sterile vial using tunable diode laser absorption spectroscopy.

PubMed

Cai, Tingdong; Gao, Guangzhen; Liu, Ying

2013-11-10

Tunable diode laser absorption measurements of pressure and H2O concentration in the headspace of vials using a distributed-feedback (DFB) diode laser near 1.4 μm are reported. A H2O line located near 7161.41 cm(-1) is selected based on its strong absorption strength and isolation from interference of neighboring transitions. Direct absorption spectra of H2O are obtained for the measurement path as well as the reference path by scanning the laser wavelength. The pressure and H2O vapor concentration in the headspace of a vial are inferred from a differential absorption signal, which is the difference between the measured and the referenced absorbance spectra. This sensor is calibration-free and no purge gas is needed. The demonstrated capability would enable measurements of pressure and H2O concentration in the headspace of vials within 2.21% and 2.86%, respectively. A precision of 1.02 Torr and 390 ppm is found for the pressure and H2O concentration, respectively. A set of measurements for commercial freeze-dried products are also performed to illustrate the usefulness of this sensor.

NIR remission spectroscopy of turbid media

NASA Astrophysics Data System (ADS)

Krauter, P.; Foschum, F.; Kienle, A.

2013-06-01

We present a method for the determination of absorption spectra in VIS and NIR spectra of turbid media without the need for calibration. Measurements of the absorption spectra of a phantom and butter are presented.

Temperature dependence of Fe/++/ crystal field spectra - Implications to mineralogical mapping of planetary surfaces

NASA Technical Reports Server (NTRS)

Sung, C.-M.; Singer, R. B.; Parkin, K. M.; Burns, R. G.; Osborne, M.

1977-01-01

Results are reported of Fe(++) crystal field spectral measurements for olivines and pyroxenes up to 400 C. The results are correlated with crystal structure data at elevated temperatures, and the validity of remote-sensed identifications of minerals on hot surfaces of the moon and Mercury is assessed. Two techniques were used to obtain spectra of minerals at elevated temperatures using a spectrophotometer. One employed a diamond cell assembly or a specially designed sample holder to measure polarized absorption spectra of heated single crystals. For the other technique, a sample holder was designed to attach to a diffuse reflectance accessory to produce reflectance spectra of heated powdered samples. Polarized absorption spectra of forsterite at 20-400 C are shown in a graph. Other graphs show the temperature dependence of Fe(++) crystal field bands in olivines, the diffuse reflectance spectra of olivine at 40-400 C, the polarization absorption spectra of orthopyroxene at 30-400 C, the diffuse reflectance spectra of pigeonite at 40-400 C, and unpolarized absorption spectra of lunar pyroxene from Apollo 15 rock 15058.

Accurate and facile determination of the index of refraction of organic thin films near the carbon 1s absorption edge.

PubMed

Yan, Hongping; Wang, Cheng; McCarn, Allison R; Ade, Harald

2013-04-26

A practical and accurate method to obtain the index of refraction, especially the decrement δ, across the carbon 1s absorption edge is demonstrated. The combination of absorption spectra scaled to the Henke atomic scattering factor database, the use of the doubly subtractive Kramers-Kronig relations, and high precision specular reflectivity measurements from thin films allow the notoriously difficult-to-measure δ to be determined with high accuracy. No independent knowledge of the film thickness or density is required. High confidence interpolation between relatively sparse measurements of δ across an absorption edge is achieved. Accurate optical constants determined by this method are expected to greatly improve the simulation and interpretation of resonant soft x-ray scattering and reflectivity data. The method is demonstrated using poly(methyl methacrylate) and should be extendable to all organic materials.

Transient and stationary spectroscopy of cytochrome c: ultrafast internal conversion controls photoreduction.

PubMed

Löwenich, Dennis; Kleinermanns, Karl; Karunakaran, Venugopal; Kovalenko, Sergey Alexander

2008-01-01

Photoreduction of cytochrome c (Cyt c) has been reinvestigated using femtosecond-to-nanosecond transient absorption and stationary spectroscopy. Femtosecond spectra of oxidized Cyt c, recorded in the probe range 270-1000 nm, demonstrate similar evolution upon 266 or 403 nm excitation: an ultrafast 0.3 ps internal conversion followed by a 4 ps vibrational cooling. Late transient spectra after 20 ps, from the cold ground-state chromophore, reveal a small but measurable signal from reduced Cyt c. The yield phi for Fe3+-->Fe2+ photoreduction is measured to be phi(403) = 0.016 and phi(266) = 0.08 for 403 and 266 nm excitation. These yields lead to a guess of the barrier E(f)(A) = 55 kJ mol(-1) for thermal ground-state electron transfer (ET). Nanosecond spectra initially show the typical absorption from reduced Cyt c and then exhibit temperature-dependent sub-microsecond decays (0.5 micros at 297 K), corresponding to a barrier E(A)(b) = 33 kJ mol(-1) for the back ET reaction and a reaction energy DeltaE = 22 kJ mol(-1). The nanosecond transients do not decay to zero on a second time scale, demonstrating the stability of some of the reduced Cyt c. The yields calculated from this stable reduced form agree with quasistationary reduction yields. Modest heating of Cyt c leads to its efficient thermal reduction as demonstrated by differential stationary absorption spectroscopy. In summary, our results point to ultrafast internal conversion of oxidized Cyt c upon UV or visible excitation, followed by Fe-porphyrin reduction due to thermal ground-state ET as the prevailing mechanism.

Fourier transform Raman spectroscopy and archaeology: a preliminary study of human teeth

NASA Astrophysics Data System (ADS)

Edwards, Howell G.; Farwell, Dennis W.; Roberts, Charlotte A.; Williams, Adrian C.

1994-01-01

The FT-Raman spectra of human bones and teeth in archaeological specimens dating to the 4th and 10th centuries AD from Romano-British and Anglo-Saxon burial sites in the U.K. have been recorded successfully using microscopic and remote sensing techniques. The samples exhibit fluorescence ascribed to mineral absorption from the grave soils but, nevertheless, good quality spectra are obtained. The versatility of the technique for non destructive sampling is demonstrated.

Diode laser differential absorption spectrometry for measurements of some parameters of condensed media.

PubMed

Liger, V V; Bolshov, M A; Kuritsyn, Yu A; Krivtsun, V M; Zybin, A V; Niemax, K

2007-04-01

A method of diode laser differential absorption spectrometry (DLDAS) is proposed. The method is based on the detection of absorption spectra variations caused by the changes of a parameter of a condensed media (temperature, composition of the components of a mixture, pH, etc.). Some simple theoretical background of the proposed technique is presented. The potentialities of the method are demonstrated in the experiments on remote contactless measurement of the temperature of aqueous solutions and measurement of the deviations of the composition of a mixture of dyes from the equilibrium state.

Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring

DTIC Science & Technology

2016-03-31

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

Determination of the Maximum Temperature in a Non-Uniform Hot Zone by Line-of-Site Absorption Spectroscopy with a Single Diode Laser.

PubMed

Liger, Vladimir V; Mironenko, Vladimir R; Kuritsyn, Yurii A; Bolshov, Mikhail A

2018-05-17

A new algorithm for the estimation of the maximum temperature in a non-uniform hot zone by a sensor based on absorption spectrometry with a diode laser is developed. The algorithm is based on the fitting of the absorption spectrum with a test molecule in a non-uniform zone by linear combination of two single temperature spectra simulated using spectroscopic databases. The proposed algorithm allows one to better estimate the maximum temperature of a non-uniform zone and can be useful if only the maximum temperature rather than a precise temperature profile is of primary interest. The efficiency and specificity of the algorithm are demonstrated in numerical experiments and experimentally proven using an optical cell with two sections. Temperatures and water vapor concentrations could be independently regulated in both sections. The best fitting was found using a correlation technique. A distributed feedback (DFB) diode laser in the spectral range around 1.343 µm was used in the experiments. Because of the significant differences between the temperature dependences of the experimental and theoretical absorption spectra in the temperature range 300⁻1200 K, a database was constructed using experimentally detected single temperature spectra. Using the developed algorithm the maximum temperature in the two-section cell was estimated with accuracy better than 30 K.

Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of gain media

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeLoach, L.D.; Page, R.H.; Wilke, G.D.

The absorption and emission properties of transition metal (TM)-doped Zinc chalcogenides have been investigated to understand their potential application as room-temperature, mid-infrared tunable laser media. Crystals of ZnS, ZnSe, and ZnTe, individually doped with Cr{sup 2+}, Co{sup 2+}, Ni{sup 2+}, or Fe{sup 2+}, have been evaluated. The absorption and emission properties are presented and discussed in terms of the energy levels from which they arise. The absorption spectra of the crystals studied exhibit strong bands between 1.4 and 2.0 {micro}m which overlap with the output of strained-layer InGaAs diodes. The room-temperature emission spectra reveal wide-band emissions from 2--3 {micro}m formore » Cr and from 2.8--1.0 {micro}m for Co. Laser demonstrations of Cr:ZnS and Cr:ZnSe have been performed in a laser-pumped laser cavity with a Co:MgF{sub 2} pump laser. The output of both lasers were determined to peak at wavelengths near 2.35 {micro}m, and both lasers demonstrated a maximum slope efficiency of approximately 20%. Based on these initial results, the Cr{sup 2+} ion is predicted to be a highly favorable laser ion for the mid-IR when doped into the zinc chalcogenides; Co{sup 2+} may also serve usefully, but laser demonstrations yet remain to be performed.« less

Absorption and emission spectroscopic characterisation of 8-amino-riboflavin

NASA Astrophysics Data System (ADS)

Tyagi, A.; Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.; Mack, M.; Ghisla, S.

2009-10-01

The flavin dye 8-amino-8-demethyl- D-riboflavin (AF) in the solvents water, DMSO, methanol, and chloroform/DMSO was studied by absorption and fluorescence spectroscopy. The first absorption band is red-shifted compared to riboflavin, and blue-shifted compared to roseoflavin (8-dimethylamino-8-demethyl-D-riboflavin). The fluorescence quantum yield of AF in the studied solvents varies between 20% and 50%. The fluorescence lifetimes were found to be in the 2-5 ns range. AF is well soluble in DMSO, weakly soluble in water and methanol, and practically insoluble in chloroform. The limited solubility causes AF aggregation, which was seen in differences between measured absorption spectra and fluorescence excitation spectra. Light scattering in the dye absorption region is discussed and approximate absorption cross-section spectra are determined from the combined measurement of transmission and fluorescence excitation spectra. The photo-stability of AF was studied by prolonged light exposure. The photo-degradation routes of AF are discussed.

Thermal denaturation of protein studied by terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Fu, Xiuhua; Li, Xiangjun; Liu, Jianjun; Du, Yong; Hong, Zhi

2012-12-01

In this study, the absorption spectra of native or thermal protein were measured in 0.2-1.4THz using terahertz time-domain spectroscopy (THz-TDS) system at room temperature, their absorption spectra and the refractive spectra were obtained. Experimental results indicate that protein both has strong absorption but their characteristics were not distinct in the THz region, and the absorption decreased during thermal denatured state. In order to prove protein had been denatured, we used Differential scanning calorimeter (DSC) measured their denatured temperature, from their DSC heating traces, collagen Td=101℃, Bovine serum albumin Td=97℃. While we also combined the Fourier transform infrared spectrometer (FTIR) to investigate their secondary and tertiary structure before and after denatuation, but the results did not have the distinct changes. We turned the absorption spectra and the refractive spectra to the dielectric spectra, and used the one-stage Debye model simulated the terahertz dielectric spectra of protein before and after denaturation. This research proved that the terahertz spectrum technology is feasible in testing protein that were affected by temperature or other factors which can provide theoretical foundation in the further study about the THz spectrum of protein and peptide temperature stability.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

X-ray absorption of a warm dense aluminum plasma created by an ultra-short laser pulse

NASA Astrophysics Data System (ADS)

Lecherbourg, L.; Renaudin, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Blancard, C.; Cossé, P.; Faussurier, G.; Shepherd, R.; Audebert, P.

2007-05-01

Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient aluminum plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum were measured for an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. A detailed opacity code using the density and temperature inferred from the FDI reproduce the measured absorption spectra except in the last stage of the recombination phase.

Ultrafast X-Ray Absorption Spectroscopy of Isochorically Heated Warm Dense Matter

NASA Astrophysics Data System (ADS)

Engelhorn, Kyle Craig

This dissertation will present a series of new tools, together with new techniques, focused on the understanding of warm and dense matter. We report on the development of a high time resolution and high detection efficiency x-ray camera. The camera is integrated with a short pulse laser and an x-ray beamline at the Advanced Light Source synchrotron. This provides an instrument for single shot, broadband x-ray absorption spectroscopy of warm and dense matter with 2 picosecond time resolution. Warm and dense matter is created by isochorically heating samples of known density with an ultrafast optical laser pulse, and X-ray absorption spectroscopy probes the unoccupied electronic density of states before the onset of hydrodynamic expansion and electron-ion equilibrium is reached. Measured spectra from a variety of materials are compared with first principle molecular dynamics and density functional theory calculations. In heated silicon dioxide spectra, two novel pre-edge features are observed, a peak below the band gap and absorption within the band gap, while a reduction was observed in the features above the edge. From consideration of the calculated spectra, the peak below the gap is attributed to valence electrons that have been promoted to the conduction band, the absorption within the gap is attributed to broken Si-O bonds, and the reduction above the edge is attributed to an elevated ionic temperature. In heated copper spectra, a time-dependent shift and broadening of the absorption edge are observed, consistent with and elevated electron temperature. The temporal evolution of the electronic temperature is accurately determined by fitting the measured spectra with calculated spectra. The electron-ion equilibration is studied with a two-temperature model. In heated nickel spectra, a shift of the absorption edge is observed. This shift is found to be inconsistent with calculated spectra and independent of incident laser fluence. A shift of the chemical potential is applied to the calculated spectra to obtain satisfactory agreement with measured spectra.

Supercontinuum generation through DNA-filled hollow core fiber for broadband absorption spectroscopy

NASA Astrophysics Data System (ADS)

Cho, Youngho; Park, Byeongho; Oh, Juyeong; Seo, Min Ah; Lee, Kwanil; Kim, Chulki; Lee, Taikjin; Woo, Deok Ha; Lee, Seok; Kim, Hyung Min; Lee, Hyuk Jae; Oh, Kyunghwan; Yeom, Dong-Il; Park, Sung Ha; Kim, Jae Hun

2015-07-01

In this study, we successfully generated the large bandwidth of supercontinuum spectra through hollow fibers filled with DNA. Also, by observing that spectra bandwidth was the widest in the order of the hollow core fiber filled with DNA modified by copper ion, the hollow core fiber with only DNA, and the bulk hollow core fiber, we demonstrated that DNA material modified with copper ions can further enhance the spectral bandwidth of supercontinuum. As a result, we anticipate that the SCG as a broadband light source can be used in analytical methods to demonstrate a wide range of biological and environmental questions.

Dynamical effects in x-ray absorption spectra of graphene and monolayered h -BN on Ni(111)

NASA Astrophysics Data System (ADS)

Rusz, J.; Preobrajenski, A. B.; Ng, May Ling; Vinogradov, N. A.; Mårtensson, N.; Wessely, O.; Sanyal, B.; Eriksson, O.

2010-02-01

We present first-principles calculations of x-ray absorption spectra of graphene and hexagonal BN monolayer on the Ni(111) substrate. Including dynamical core-hole screening effects according to the theory of Mahan-Nozières-de Dominics (MND) results in an overall good agreement with previously published experimental data and our new observations. This approach provides a unified first-principles description of the electronic structure and core excitations in the sp2 -bonded materials on metal surfaces and a better insight into the dynamics of screening effects. We demonstrate in particular that the observed spectral features of graphene and hexagonal BN can be well reproduced with the MND theory, and that they are determined by a delicate balance between initial and final-state effects.

A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest

PubMed Central

Dahlberg, Peter D.; Boughter, Christopher T.; Faruk, Nabil F.; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A.; Sherani, Aiman; Hammond, Adam T.

2016-01-01

A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH3NH3PbBr3 perovskites and measure differences between nanocrystal films and micron scale crystals. PMID:27910631

Heterodyne Receiver for Laboratory Spectrosocpy of Molecules of Astrophysical Importance

NASA Astrophysics Data System (ADS)

Wehres, Nadine; Lewen, Frank; Endres, Christian; Hermanns, Marius; Schlemmer, Stephan

2016-06-01

We present first results of a heterodyne receiver built for high-resolution emission laboratory spectroscopy of molecules of astrophysical interest. The room-temperature receiver operates at frequencies between 80 and 110 GHz, consistent with ALMA band 3. Many molecules have been identified in the interstellar and circumstellar medium at exactly these frequencies by comparing emission spectra obtained from telescopes to high-resolution laboratory absorption spectra. Taking advantage of the recent progresses in the field of mm/submm technology in the astronomy community, we have built a room-temperature emission spectrometer making use of heterodyne receiver technology at an instantaneous bandwidth of currently 2.5 GHz. The system performance, in particular the noise temperature and systematic errors, is presented. The proof-of-concept is demonstrated by comparing the emission spectrum of methyl cyanide to respective absorption spectra and to the literature. Future prospects as well as limitations of the new laboratory receiver for the spectroscopy of complex organic molecules or transient species in discharges will be discussed.

Transient Spectra in TDDFT: Corrections and Correlations

NASA Astrophysics Data System (ADS)

Parkhill, John; Nguyen, Triet

We introduce an atomistic, all-electron, black-box electronic structure code to simulate transient absorption (TA) spectra and apply it to simulate pyrazole and a GFP chromophore derivative. The method is an application of OSCF2, our dissipative extension of time-dependent density functional theory. We compare our simulated spectra directly with recent ultra-fast spectroscopic experiments, showing that they are usefully predicted. We also relate bleaches in the TA signal to Fermi-blocking which would be missed in a simplified model. An important ingredient in the method is the stationary-TDDFT correction scheme recently put forwards by Fischer, Govind, and Cramer which allows us to overcome a limitation of adiabatic TDDFT. We demonstrate that OSCF2 is able to predict both the energies of bleaches and induced absorptions, as well as the decay of the transient spectrum, with only the molecular structure as input. With remaining time we will discuss corrections which resolve the non-resonant behavior of driven TDDFT, and correlated corrections to mean-field dynamics.

Investigation of periodically driven systems by x-ray absorption spectroscopy using asynchronous data collection mode

NASA Astrophysics Data System (ADS)

Singh, H.; Donetsky, D.; Liu, J.; Attenkofer, K.; Cheng, B.; Trelewicz, J. R.; Lubomirsky, I.; Stavitski, E.; Frenkel, A. I.

2018-04-01

We report the development, testing, and demonstration of a setup for modulation excitation spectroscopy experiments at the Inner Shell Spectroscopy beamline of National Synchrotron Light Source - II. A computer algorithm and dedicated software were developed for asynchronous data processing and analysis. We demonstrate the reconstruction of X-ray absorption spectra for different time points within the modulation pulse using a model system. This setup and the software are intended for a broad range of functional materials which exhibit structural and/or electronic responses to the external stimulation, such as catalysts, energy and battery materials, and electromechanical devices.

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwasa, Takeshi, E-mail: tiwasa@mail.sci.hokudai.ac.jp; Takenaka, Masato; Taketsugu, Tetsuya

A theoretical method to compute infrared absorption spectra when a molecule is interacting with an arbitrary nonuniform electric field such as near-fields is developed and numerically applied to simple model systems. The method is based on the multipolar Hamiltonian where the light-matter interaction is described by a spatial integral of the inner product of the molecular polarization and applied electric field. The computation scheme is developed under the harmonic approximation for the molecular vibrations and the framework of modern electronic structure calculations such as the density functional theory. Infrared reflection absorption and near-field infrared absorption are considered as model systems.more » The obtained IR spectra successfully reflect the spatial structure of the applied electric field and corresponding vibrational modes, demonstrating applicability of the present method to analyze modern nanovibrational spectroscopy using near-fields. The present method can use arbitral electric fields and thus can integrate two fields such as computational chemistry and electromagnetics.« less

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy.

PubMed

Iwasa, Takeshi; Takenaka, Masato; Taketsugu, Tetsuya

2016-03-28

A theoretical method to compute infrared absorption spectra when a molecule is interacting with an arbitrary nonuniform electric field such as near-fields is developed and numerically applied to simple model systems. The method is based on the multipolar Hamiltonian where the light-matter interaction is described by a spatial integral of the inner product of the molecular polarization and applied electric field. The computation scheme is developed under the harmonic approximation for the molecular vibrations and the framework of modern electronic structure calculations such as the density functional theory. Infrared reflection absorption and near-field infrared absorption are considered as model systems. The obtained IR spectra successfully reflect the spatial structure of the applied electric field and corresponding vibrational modes, demonstrating applicability of the present method to analyze modern nanovibrational spectroscopy using near-fields. The present method can use arbitral electric fields and thus can integrate two fields such as computational chemistry and electromagnetics.

Outbursts by low-mass white dwarfs in symbiotic variables

NASA Technical Reports Server (NTRS)

Sion, Edward M.; Ready, Christian J.

1992-01-01

The high-resolution IUE spectra of the symbiotic variables BF Cygni and EG Andromedae are studied in order to describe the P Cygni-like features of these objects. The 10 high-dispersion IUE spectra are examined for orbital phase-dependent variations in the C IV resonance doublet in terms of velocity and/or structure. One image is found to have a strong He-II absorption feature that coincides in velocity with the C-IV absorption component in P Cygni. The absorbing material for both lines is related to outflow and P Cygni self-absorption near the hot component. The P Cygni profiles do not appear to be related to a red-giant wind nor an expanding circumbinary shell in the in both BF Cyg and EG And. Quasi-static evolutionary model calculations demonstrate an unexpected outburst behavior in response to the assumed accretion. These data are shown to be important for the study of symbiotic systems that contain low-mass white dwarfs.

Theoretical Prediction of Si 2–Si 33 Absorption Spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Li -Zhen; Lu, Wen -Cai; Qin, Wei

Here, the optical absorption spectra of Si 2–Si 33 clusters were systematically studied by a time-dependent density functional theory approach. The calculations revealed that the absorption spectrum becomes significantly broad with increasing cluster size, stretching from ultraviolet to the infrared region. The absorption spectra are closely related to the structural motifs. With increasing cluster size, the absorption intensity of cage structures gradually increases, but the absorption curves of the prolate and the Y-shaped structures are very sensitive to cluster size. If the transition energy reaches ~12 eV, it is noted that all the clusters have remarkable absorption in deep ultravioletmore » region of 100–200 nm, and the maximum absorption intensity is ~100 times that in the visible region. Further, the optical responses to doping in the Si clusters were studied.« less

Theoretical Prediction of Si 2–Si 33 Absorption Spectra

DOE PAGES

Zhao, Li -Zhen; Lu, Wen -Cai; Qin, Wei; ...

2017-07-07

Here, the optical absorption spectra of Si 2–Si 33 clusters were systematically studied by a time-dependent density functional theory approach. The calculations revealed that the absorption spectrum becomes significantly broad with increasing cluster size, stretching from ultraviolet to the infrared region. The absorption spectra are closely related to the structural motifs. With increasing cluster size, the absorption intensity of cage structures gradually increases, but the absorption curves of the prolate and the Y-shaped structures are very sensitive to cluster size. If the transition energy reaches ~12 eV, it is noted that all the clusters have remarkable absorption in deep ultravioletmore » region of 100–200 nm, and the maximum absorption intensity is ~100 times that in the visible region. Further, the optical responses to doping in the Si clusters were studied.« less

Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patanen, M.; Benkoula, S.; Nicolas, C.

2015-09-28

Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, B.; Japan Science and Technology Agency, CREST, 5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075; Katan, C.

This study demonstrates a measurement system for a non-degenerate two-photon absorption (NDTPA) spectrum. The NDTPA light sources are a white light super continuum beam (WLSC, 500 ∼ 720 nm) and a fundamental beam (798 nm) from a Ti:Sapphire laser. A reliable broadband NDTPA spectrum is acquired in a single-shot detection procedure using a 128-channel lock-in amplifier. The NDTPA spectra for several common laser dyes are measured. Two photon absorption cross section enhancements are found in the experiment and validated by theoretical calculation for all of the chromophores.

DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

DTIC Science & Technology

2017-10-31

of isolated molecules and that of bulk systems. DFT calculated absorption spectra represent quantitative estimates that can be correlated with...spectra, can be correlated with the presence of these hydrocarbons (see reference [1]). Accordingly, the molecular structure and IR absorption spectra of...associated with different types of ambient molecules, e.g., H2O, in order to apply background subtraction or spectral-signature- correlation algorithms

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

DTIC Science & Technology

2016-06-03

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

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

2014-05-29

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 (σ p and σ m ). 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.

Calculation of density functional theory (DFT) vibrational parameters of nucleotides for use in theoretical optical calculations: Herein applied to circular dichroism (CD) and absorption of polynucleotides

NASA Astrophysics Data System (ADS)

Ferber, Steven Dwight

2005-11-01

The Vibrational Circular Dichroism (VCD) of Nucleic Acids is a sensitive function of their conformation. DeVoe's classically derived polarizability theory allows the calculation of polymer absorption and circular dichroism spectra in any frequency range. Following the approach of Tinoco and Cech as modified by Moore and Self, calculations were done in the infrared (IR) region with theoretically derived monomer input parameters. Presented herein are calculated absorption and CD spectra for nucleic acid oligomers and polymers. These calculations improve upon earlier attempts, which utilized frequencies, intensities and normal modes from empirical analysis of the nitrogenous base of the monomers. These more complete input polarizability parameters include all contributions to specific vibrational normal modes for the entire nucleotide structure. They are derived from density functional theory (DFT) vibrational analysis on quasi-nucleotide monomers using the GAUSSIAN '98/'03 program. The normal modes are "integrated" for the first time into single virtual (DeVoe) oscillators by incorporating "fixed partial charges" in the manner of Schellman. The results include the complete set of monomer normal modes. All of these modes may be analyzed, in a manner similar to those demonstrated here (for the 1500-1800 cm-1 region). A model is utilized for the polymer/oligomer monomers which maintains the actual electrostatic charge on the adjacent protonated phosphoryl groups (hydrogen phosphate, a mono-anion). This deters the optimization from "collapsing" into a hydrogen-bonded "ball" and thereby maintains the extended (polymer-like) conformation. As well, the precise C2 "endo" conformation of the sugar ring is maintained in the DNA monomers. The analogous C3 "endo" conformation is also maintained for the RNA monomers, which are constrained by massive "anchors" at the phosphates. The complete IR absorbance spectra (0-4,000 cm-1) are calculated directly in Gaussian. Calculated VCD and Absorbance Spectra for the eight standard Ribonucleic and Deoxy-ribonucleic acid homo-polymers in the nitrogenous base absorbing region 1550-1750 cm-1 are presented. These spectra match measured spectra at least as well as spectra calculated from empirical parameters. These results demonstrate that the purely theoretical calculation, an example given herein, should serve to provide more transferable, universal parameters for the polarizability treatment of the optical properties of oligomers and polymers.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sargent, B. A.; Forrest, W.; Watson, Dan M.

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

Realistic absorption coefficient of ultrathin films

NASA Astrophysics Data System (ADS)

Cesaria, M.; Caricato, A. P.; Martino, M.

2012-10-01

Both a theoretical algorithm and an experimental procedure are discussed of a new route to determine the absorption/scattering properties of thin films deposited on transparent substrates. Notably, the non-measurable contribution of the film-substrate interface is inherently accounted for. While the experimental procedure exploits only measurable spectra combined according to a very simple algorithm, the theoretical derivation does not require numerical handling of the acquired spectra or any assumption on the film homogeneity and substrate thickness. The film absorption response is estimated by subtracting the measured absorption spectrum of the bare substrate from that of the film on the substrate structure but in a non-straightforward way. In fact, an assumption about the absorption profile of the overall structure is introduced and a corrective factor accounting for the relative film-to-substrate thickness. The method is tested on films of a well known material (ITO) as a function of the film structural quality and influence of the film-substrate interface, both deliberately changed by thickness tuning and doping. Results are found fully consistent with information obtained by standard optical analysis and band gap values reported in the literature. Additionally, comparison with a conventional method demonstrates that our route is generally more accurate even if particularly suited for very thin films.

Spectroscopy in Large Lecture Halls, II.

ERIC Educational Resources Information Center

Juergens, Frederick H.

1988-01-01

Describes a method for demonstrating absorption spectra of intensely colored solutions using a mounted grating and a specially designed cell. Allows a student to compare the spectrum of a white light source directly with the same light modified by an absorbing spectrum. Uses acrylic tubing to make the cell. (MVL)

Hierarchy of stochastic Schrödinger equation towards the calculation of absorption and circular dichroism spectra.

PubMed

Ke, Yaling; Zhao, Yi

2017-05-07

A theoretically solid and numerically exact method is presented for the calculation of absorption and circular dichroism (CD) spectra of molecular aggregates immersed in a harmonic bath constituted as the combination of some prominent quantized vibrational modes and continuous overdamped Brownian oscillators. The feasibility and the validity of newly proposed method are affirmed in the analytical monomer spectra. To go beyond the independent local bath approximation, all the correlations of site energy fluctuations and excitonic coupling fluctuations are included in our strategy, and their influence on the absorption and CD spectra is investigated based on the Frenkel exciton model of homodimer. In the end, a good fit of the absorption and part of CD spectra for the entire B800-B850 ring in the light-harvesting complexes 2 of purple bacteria to the experimental data is given, and the simulation results suggest that the asymmetry in the 800 nm region of CD spectra is actually an indication of B800-B850 inter-ring coupling.

TD-M06-2X insights into the absorption and emission spectra of dichlorvos and its molecularly imprinted recognition by methacrylic acid.

PubMed

Cheng, Xueli

2016-11-01

The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in methanol, water, and chloroform in the molecularly imprinted recognition were investigated systematically. The M06-2X results revealed that: 1) the hydroxyl groups in polar solvents such as methanol and water may markedly influence the weak interactions, and then alter the adsorption and emission spectra; 2) the electronic excitation in absorption spectra of dichlorvos is dominated by the configuration HOMO → LUMO, but in the most stable dichlorvos-MAA it becomes the ππ* excitation of HOMO → LUMO + 1; 3) Mulliken charges reveal that dichlorvos almost dissociates to Cl - and a cation in its S 1 excitation state; 4) the phosphorescence spectra of dichlorvos-MAA are relatively weak. Graphical Abstract The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in the molecularly imprinted recognition of dichlorvos were investigated systematically in methanol, water, and chloroform as solvents.

Unified analysis of optical absorption spectra of carotenoids based on a stochastic model.

PubMed

Uragami, Chiasa; Saito, Keisuke; Yoshizawa, Masayuki; Molnár, Péter; Hashimoto, Hideki

2018-05-03

The chemical structures of the carotenoid molecules are very simple and one might think that the electronic feature of it is easily predicted. However, it still has so much unknown information except the correlation between the electronic energy state and the length of effective conjugation chain of carotenoids. To investigate the electronic feature of the carotenoids, the most essential method is measuring the optical absorption spectra, but simulating it from the resonance Raman spectra is also the effective way. From this reason, we studied the optical absorption spectra as well as resonance Raman spectra of 15 different kinds of cyclic carotenoid molecules, recorded in tetrahydrofuran (THF) solutions at room temperature. The whole band shapes of the absorption spectra of all these carotenoid molecules were successfully simulated based on a stochastic model using Brownian oscillators. The parameters obtained from the simulation made it possible to discuss the intermolecular interaction between carotenoids and solvent THF molecules quantitatively. Copyright © 2018. Published by Elsevier Inc.

Hierarchy of stochastic Schrödinger equation towards the calculation of absorption and circular dichroism spectra

NASA Astrophysics Data System (ADS)

Ke, Yaling; Zhao, Yi

2017-05-01

A theoretically solid and numerically exact method is presented for the calculation of absorption and circular dichroism (CD) spectra of molecular aggregates immersed in a harmonic bath constituted as the combination of some prominent quantized vibrational modes and continuous overdamped Brownian oscillators. The feasibility and the validity of newly proposed method are affirmed in the analytical monomer spectra. To go beyond the independent local bath approximation, all the correlations of site energy fluctuations and excitonic coupling fluctuations are included in our strategy, and their influence on the absorption and CD spectra is investigated based on the Frenkel exciton model of homodimer. In the end, a good fit of the absorption and part of CD spectra for the entire B800-B850 ring in the light-harvesting complexes 2 of purple bacteria to the experimental data is given, and the simulation results suggest that the asymmetry in the 800 nm region of CD spectra is actually an indication of B800-B850 inter-ring coupling.

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

DTIC Science & Technology

2013-08-20

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--13-9479 Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using ...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density...structure associated with Fe, Mn, and Mg water complexes using time-dependent density functional theory (TD-DFT). Calculation of excited state resonance

Simulation of Near-Edge X-ray Absorption Fine Structure with Time-Dependent Equation-of-Motion Coupled-Cluster Theory.

PubMed

Nascimento, Daniel R; DePrince, A Eugene

2017-07-06

An explicitly time-dependent (TD) approach to equation-of-motion (EOM) coupled-cluster theory with single and double excitations (CCSD) is implemented for simulating near-edge X-ray absorption fine structure in molecular systems. The TD-EOM-CCSD absorption line shape function is given by the Fourier transform of the CCSD dipole autocorrelation function. We represent this transform by its Padé approximant, which provides converged spectra in much shorter simulation times than are required by the Fourier form. The result is a powerful framework for the blackbox simulation of broadband absorption spectra. K-edge X-ray absorption spectra for carbon, nitrogen, and oxygen in several small molecules are obtained from the real part of the absorption line shape function and are compared with experiment. The computed and experimentally obtained spectra are in good agreement; the mean unsigned error in the predicted peak positions is only 1.2 eV. We also explore the spectral signatures of protonation in these molecules.

X-Ray Absorption Spectroscopy As a Probe of Microbial Sulfur Biochemistry: the Nature of Bacterial Sulfur Globules Revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, G.N.; Gnida, M.; Bazylinski, D.A.

2009-05-18

The chemical nature of the sulfur in bacterial sulfur globules has been the subject of controversy for a number of years. Sulfur K-edge X-ray absorption spectroscopy (XAS) is a powerful technique for probing the chemical forms of sulfur in situ, but two groups have used it with very different conclusions. The root of the controversy lies with the different detection strategies used by the two groups, which result in very different spectra. This paper seeks to resolve the controversy. We experimentally demonstrate that the use of transmittance detection for sulfur K-edge XAS measurements is highly prone to spectroscopic distortions andmore » that much of the published work on sulfur bacteria is very likely based on distorted data. We also demonstrate that all three detection methods used for X-ray absorption experiments yield essentially identical spectra when the measurements are carried out under conditions where no experimental distortions are expected. Finally, we turn to the original question--the chemical nature of bacterial sulfur. We examine isolated sulfur globules of Allochromatium vinosum and intact cells of a strain of magnetotactic coccus and show that XAS indicates the presence of a chemical form of sulfur resembling S{sub 8}.« less

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

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell.

PubMed

Hong, Xinguo; Newville, Matthew; Prakapenka, Vitali B; Rivers, Mark L; Sutton, Stephen R

2009-07-01

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within +/-3 degrees relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, X.; Newville, M.; Prakapenka, V.B.

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over amore » small angular range of DAC orientation, e.g., within {+-}3{sup o} relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO{sub 2} recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO{sub 2} glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO{sub 2} glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.« less

Excitation of photosystem I by 760 nm femtosecond laser pulses: transient absorption spectra and intermediates

NASA Astrophysics Data System (ADS)

Cherepanov, Dmitry A.; Shelaev, Ivan V.; Gostev, Fedor E.; Mamedov, Mahir D.; Petrova, Anastasia A.; Aybush, Arseniy V.; Shuvalov, Vladimir A.; Semenov, Alexey Yu; Nadtochenko, Victor A.

2017-09-01

Excitation of photosystem I (PS I) by a femtosecond 760 nm pump leads to one- and two-photon absorption. The one-photon excitation produces intermediates with transient absorption spectra similar to the spectra of the primary [{{{P}}700}+{{{A}}0}-{{A}}1] and secondary [{{{P}}700}+{{A}}0{{{A}}1}-] ion-radical pairs in the PS I reaction center. The two-photon absorption generates the upper level excited states of chlorophyll (Chl) and carotenoid molecules in the antenna. These excited states are converted into the long-lived intermediates and can be tentatively attributed to the excited and charge-transfer ion-radical states of Chl molecules and to the excited states of carotenoids in the antenna. The transient spectra of intermediates generated by two-photon excitation differ from the transient one-photon spectra of the primary and secondary ion-radical pairs.

Enhanced broadband near-infrared luminescence from Pr3+-doped tellurite glass with silver nanoparticles

NASA Astrophysics Data System (ADS)

Cheng, Pan; Zhou, Yaxun; Zhou, Minghan; Su, Xiue; Zhou, Zizhong; Yang, Gaobo

2017-11-01

Pr3+-doped tellurite glasses containing metallic silver NPs were synthesized by the conventional melt-quenching technique. Structural, thermal and optical properties of the synthesized glass samples were characterized by X-Ray diffraction (XRD) curves, Raman spectra, differential scanning calorimeter (DSC) curves, transmission electron microscopy (TEM) images, UV/Vis/NIR absorption and near-infrared fluorescence emission spectra. The XRD curves confirmed the amorphous structural nature of the synthesized glasses, the Raman spectra identified the presence of different vibrational groups, the DSC curves verified the good thermal stability, and the TEM images revealed the nucleated silver NPs with average diameter about 10 nm dispersed in the glass matrix and its surface Plasmon resonance (SPR) absorption band was located at around 510 nm. Besides, Judd-Ofelt intensity parameters Ωt (t = 2, 4, 6) and other important spectroscopic parameters like transition probability, radiative lifetime, branching ratio were calculated to evaluate the radiative properties of Pr3+ levels from the measured optical absorption spectra. It was found that Pr3+-doped tellurite glasses could emit an ultra-broadband fluorescence extending from 1250 to 1650 nm under the 488 nm excitation, and this fluorescence emission increased further with the introduction of silver NPs. The enhanced fluorescence was mainly attributed to the increased local electric field around Pr3+ induced by silver NPs. The present results demonstrate that Pr3+-Ag codoped tellurite glass is a promising candidate for the near-infrared band ultra-broadband fiber amplifiers covering the expanded low-loss communication window.

Comparative Studies in the Fluorescence and Excitation Spectra of 3-Hydroxyflavone and 2(2 '-Heteroaryl)-3-Hydroxy-4H-Chromen-4-Ones

NASA Astrophysics Data System (ADS)

Kaur, R.; Kaur, K.; Bansal, M.

2017-05-01

The absorption, fluorescence, and excitation spectra of FHC and THC have been studied and compared with 3HF in cyclohexane, acetonitrile, and methanol. Anion formation in acetonitrile and methanol has been observed in all three flavonols in the order THC-FHC-3HF in their ground states. As excitation and absorption spectra are similar in all the cases (including the anion one), it is possible to observe the absorption spectra of the pure anion of the flavonols in neutral solvents, which is difficult to measure directly.

On the limitations of statistical absorption studies with the Sloan Digital Sky Surveys I-III

NASA Astrophysics Data System (ADS)

Lan, Ting-Wen; Ménard, Brice; Baron, Dalya; Johnson, Sean; Poznanski, Dovi; Prochaska, J. Xavier; O'Meara, John M.

2018-07-01

We investigate the limitations of statistical absorption measurements with the Sloan Digital Sky Survey (SDSS) optical spectroscopic surveys. We show that changes in the data reduction strategy throughout different data releases have led to a better accuracy at long wavelengths, in particular for sky line subtraction, but a degradation at short wavelengths with the emergence of systematic spectral features with an amplitude of about 1 per cent. We show that these features originate from inaccuracy in the fitting of modelled F-star spectra used for flux calibration. The best-fitting models for those stars are found to systematically overestimate the strength of metal lines and underestimate that of Lithium. We also identify the existence of artefacts due to masking and interpolation procedures at the wavelengths of the hydrogen Balmer series leading to the existence of artificial Balmer α absorption in all SDSS optical spectra. All these effects occur in the rest frame of the standard stars and therefore present Galactic longitude variations due to the rotation of the Galaxy. We demonstrate that the detection of certain weak absorption lines reported in the literature is solely due to calibration effects. Finally, we discuss new strategies to mitigate these issues.

On the limitations of statistical absorption studies with the Sloan Digital Sky Surveys I-III

NASA Astrophysics Data System (ADS)

Lan, Ting-Wen; Ménard, Brice; Baron, Dalya; Johnson, Sean; Poznanski, Dovi; Prochaska, J. Xavier; O'Meara, John M.

2018-04-01

We investigate the limitations of statistical absorption measurements with the SDSS optical spectroscopic surveys. We show that changes in the data reduction strategy throughout different data releases have led to a better accuracy at long wavelengths, in particular for sky line subtraction, but a degradation at short wavelengths with the emergence of systematic spectral features with an amplitude of about one percent. We show that these features originate from inaccuracy in the fitting of modeled F-star spectra used for flux calibration. The best-fit models for those stars are found to systematically over-estimate the strength of metal lines and under-estimate that of Lithium. We also identify the existence of artifacts due to masking and interpolation procedures at the wavelengths of the hydrogen Balmer series leading to the existence of artificial Balmer α absorption in all SDSS optical spectra. All these effects occur in the rest-frame of the standard stars and therefore present Galactic longitude variations due to the rotation of the Galaxy. We demonstrate that the detection of certain weak absorption lines reported in the literature are solely due to calibration effects. Finally, we discuss new strategies to mitigate these issues.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra.

PubMed

Vilas, F; Gaffey, M J

1989-11-10

Absorption features having depths up to 5% are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra

NASA Technical Reports Server (NTRS)

Vilas, Faith; Gaffey, Michael J.

1989-01-01

Absorption features having depths up to 5 percent are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

More on the lambda 2800 A 'interstellar extinction' feature

NASA Astrophysics Data System (ADS)

McLachlan, A.; Nandy, K.

1985-02-01

In a response made to a recent letter by Karim et al. (1984), it is shown that the examples of interstellar absorption at 2800 A that they attribute to proteinaceous material can all be attributed to overexposure of IUE detectors. It is pointed out that stars in the Large Magellanic Cloud show pronounced absorption at 2800 A which cannot be due to interstellar protein since there is no associated absorption at 2200 A; this lack of absorption cannot be due to presence of graphite, whose absorption is weak in the Cloud. The claim by Karim et al. that the spectra of eight stars show 2800 A absorption and that these spectra are saturation-free is considered, and it is shown that data processing problems at IUE ground stations make these spectra unreliable.

Terahertz sensing of highly absorptive water-methanol mixtures with multiple resonances in metamaterials.

PubMed

Chen, Min; Singh, Leena; Xu, Ningning; Singh, Ranjan; Zhang, Weili; Xie, Lijuan

2017-06-26

Terahertz sensing of highly absorptive aqueous solutions remains challenging due to strong absorption of water in the terahertz regime. Here, we experimentally demonstrate a cost-effective metamaterial-based sensor integrated with terahertz time-domain spectroscopy for highly absorptive water-methanol mixture sensing. This metamaterial has simple asymmetric wire structures that support multiple resonances including a fundamental Fano resonance and higher order dipolar resonance in the terahertz regime. Both the resonance modes have strong intensity in the transmission spectra which we exploit for detection of the highly absorptive water-methanol mixtures. The experimentally characterized sensitivities of the Fano and dipole resonances for the water-methanol mixtures are found to be 160 and 305 GHz/RIU, respectively. This method provides a robust route for metamaterial-assisted terahertz sensing of highly absorptive chemical and biochemical materials with multiple resonances and high accuracy.

On the inclusion of the hydrogen dimer in the analysis of Voyager IRIS spectra

NASA Technical Reports Server (NTRS)

Carlson, Barbara E.; Ma, Qiancheng; Lacis, Andrew

1992-01-01

Empirical formulas are fitted to existing theoretical absorption spectra of H2-H2 pairs in the far-infrared allowing the inclusion of dimer absorption, parameterized with the height dependence of the para-hydrogen profile, in the calculations. Comparison between synthetic and Voyager IRIS spectra shows that once the dimer absorption is included it is now possible to reproduce the hydrogen portion of the IRIS spectrum to within the precision of the measurements.

Polarization-sensitive nanowire photodetectors based on solution-synthesized CdSe quantum-wire solids.

PubMed

Singh, Amol; Li, Xiangyang; Protasenko, Vladimir; Galantai, Gabor; Kuno, Masaru; Xing, Huili Grace; Jena, Debdeep

2007-10-01

Polarization-sensitive photodetectors are demonstrated using solution-synthesized CdSe nanowire (NW) solids. Photocurrent action spectra taken with a tunable white light source match the solution linear absorption spectra of the NWs, showing that the NW network is responsible for the device photoconductivity. Temperature-dependent transport measurements reveal that carriers responsible for the dark current through the nanowire solids are thermally excited across CdSe band gap. The NWs are aligned using dielectrophoresis between prepatterned electrodes using conventional optical photolithography. The photocurrent through the NW solid is found to be polarization-sensitive, consistent with complementary absorption (emission) measurements of both single wires and their ensembles. The range of solution-processed semiconducting NW materials, their facile synthesis, ease of device fabrication, and compatibility with a variety of substrates make them attractive for potential nanoscale polarization-sensitive photodetectors.

Rapid determination of saponification value and polymer content of vegetable and fish oils by terahertz spectroscopy.

PubMed

Jiang, Feng Ling; Ikeda, Ikuo; Ogawa, Yuichi; Endo, Yasushi

2012-01-01

A rapid method for determining the saponification value (SV) and polymer content of vegetable and fish oils using the terahertz (THz) spectroscopy was developed. When the THz absorption spectra for vegetable and fish oils were measured in the range of 20 to 400 cm⁻¹, two peaks were seen at 77 and 328 cm⁻¹. The level of absorbance at 77 cm⁻¹ correlated well with the SV. When the THz absorption spectra of thermally treated high-oleic safflower oils were measured, the absorbance increased with heating time. The polymer content in thermally treated oil correlated with the absorbance at 77 cm⁻¹. These results demonstrate that the THz spectrometry is a suitable non-destructive technique for the rapid determination of the SV and polymer content of vegetable and fish oils.

Sensitivity and resolution in frequency comb spectroscopy of buffer gas cooled polyatomic molecules

NASA Astrophysics Data System (ADS)

Changala, P. Bryan; Spaun, Ben; Patterson, David; Doyle, John M.; Ye, Jun

2016-12-01

We discuss the use of cavity-enhanced direct frequency comb spectroscopy in the mid-infrared region with buffer gas cooling of polyatomic molecules for high-precision rovibrational absorption spectroscopy. A frequency comb coupled to an optical enhancement cavity allows us to collect high-resolution, broad-bandwidth infrared spectra of translationally and rotationally cold (10-20 K) gas-phase molecules with high absorption sensitivity and fast acquisition times. The design and performance of the combined apparatus are discussed in detail. Recorded rovibrational spectra in the CH stretching region of several organic molecules, including vinyl bromide (CH_2CHBr), adamantane (C_{10}H_{16}), and diamantane (C_{14}H_{20}) demonstrate the resolution and sensitivity of this technique, as well as the intrinsic challenges faced in extending the frontier of high-resolution spectroscopy to large complex molecules.

On the nature of absorption features toward nearby stars

NASA Astrophysics Data System (ADS)

Kohl, S.; Czesla, S.; Schmitt, J. H. M. M.

2016-06-01

Context. Diffuse interstellar absorption bands (DIBs) of largely unknown chemical origin are regularly observed primarily in distant early-type stars. More recently, detections in nearby late-type stars have also been claimed. These stars' spectra are dominated by stellar absorption lines. Specifically, strong interstellar atomic and DIB absorption has been reported in τ Boo. Aims: We test these claims by studying the strength of interstellar absorption in high-resolution TIGRE spectra of the nearby stars τ Boo, HD 33608, and α CrB. Methods: We focus our analysis on a strong DIB located at 5780.61 Å and on the absorption of interstellar Na. First, we carry out a differential analysis by comparing the spectra of the highly similar F-stars, τ Boo and HD 33608, whose light, however, samples different lines of sight. To obtain absolute values for the DIB absorption, we compare the observed spectra of τ Boo, HD 33608, and α CrB to PHOENIX models and carry out basic spectral modeling based on Voigt line profiles. Results: The intercomparison between τ Boo and HD 33608 reveals that the difference in the line depth is 6.85 ± 1.48 mÅ at the DIB location which is, however, unlikely to be caused by DIB absorption. The comparison between PHOENIX models and observed spectra yields an upper limit of 34.0 ± 0.3 mÅ for any additional interstellar absorption in τ Boo; similar results are obtained for HD 33608 and α CrB. For all objects we derive unrealistically large values for the radial velocity of any presumed interstellar clouds. In τ Boo we find Na D absorption with an equivalent width of 0.65 ± 0.07 mÅ and 2.3 ± 0.1 mÅ in the D2 and D1 lines. For the other Na, absorption of the same magnitude could only be detected in the D2 line. Our comparisons between model and data show that the interstellar absorption toward τ Boo is not abnormally high. Conclusions: We find no significant DIB absorption in any of our target stars. Any differences between modeled and observed spectra are instead attributable to inaccuracies in the stellar atmospheric modeling than to DIB absorption. The spectra are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/591/A20

Fiber optic FTIR instrument for in vivo detection of colonic neoplasia

NASA Astrophysics Data System (ADS)

Van Nortwick, Matthew; Hargrove, John; Wolters, Rolf; Crawford, James M.; Arroyo, May; Mackanos, Mark; Contag, Christopher H.; Wang, Thomas D.

2009-02-01

We demonstrate the proof of concept for use of a fiber optic FTIR instrument to perform in vivo detection of colonic neoplasia as an adjunct to medical endoscopy. FTIR is sensitive to the molecular composition of tissue, and can be used as a guide for biopsy by identifying pre-malignant tissue (dysplasia). First, we demonstrate the use of a silver halide optical fiber to collect mid-infrared absorption spectra in the 950 to 1800 cm-1 regime with high signal-to-noise from biopsy specimens of colonic mucosa tissue ex vivo. We observed subtle differences in wavenumber and magnitude of the absorbance peaks over this regime. We then show that optimal sub-ranges can be defined within this spectral regime and that spectral pre-processing can be performed to classify the tissue as normal, hyperplasia, or dysplasia with high levels of performance. We used a partial least squares discriminant analysis and a leave-one-subject-out crossvalidation strategy to classify the spectra. The results were compared with histology, and the optimal thresholds resulted in an overall sensitivity, specificity, accuracy, and positive predictive value of 96%, 92%, 93%, and 82%, respectively for this technique. We demonstrate that mid-infrared absorption spectra can be collected remotely with an optical fiber and used to identify colonic dysplasia with high accuracy. We are now developing an endoscope compatible optical fiber to use this technique clinically for the early detection of cancer.

Computational study of the absorption spectrum of defected ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Michos, F. I.; Sigalas, M. M.

2018-04-01

Energy levels and absorption spectra of defected ZnS nanoparticles (NPs) were calculated with Density Functional Theory (DFT) and Time Dependent DFT. Several types of defects were examined such as vacancies and substitutions. NPs with S vacancies were found to have their absorption spectra moved to lower energies well inside the visible spectrum with significantly high oscillator strength. Also, NPs with substitution of S atoms with Cl, Br, or I showed significant absorption. In general, this type of defect moves the absorption spectra in lower energies, thus bringing the absorption edge into the visible spectrum, while the unperturbed NPs have absorption edges in the UV region. In addition, ZnS NPs are made from more abundant and less toxic elements than the more commonly used CdSe NPs. For that reason, they may find significant applications in solar cells and other photonic applications, as well as in biosensing applications as biomarkers.

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

PubMed

Jensen, Peter Snoer; Bak, Jimmy; Andersson-Engels, Stefan

2003-01-01

Near- and mid-infrared absorption spectra of pure water and aqueous 1.0 g/dL glucose solutions in the wavenumber range 8000-950 cm-1 were measured in the temperature range 30-42 degrees C in steps of 2 degrees C. Measurements were carried out with an FT-IR spectrometer and a variable pathlength transmission cell controlled within 0.02 degree C. Pathlengths of 50 microns and 0.4 mm were used in the mid- and near-infrared spectral region, respectively. Difference spectra were used to determine the effect of temperature on the water spectra quantitatively. These spectra were obtained by subtracting the 37 degrees C water spectrum from the spectra measured at other temperatures. The difference spectra reveal that the effect of temperature is highest in the vicinity of the strong absorption bands, with a number of isosbestic points with no temperature dependence and relatively flat plateaus in between. On the basis of these spectra, prospects for and limitations on data analysis for infrared diagnostic methods are discussed. As an example, the absorptive properties of glucose were studied in the same temperature range in order to determine the effect of temperature on the spectral shape of glucose. The change in water absorption associated with the addition of glucose has also been studied. An estimate of these effects is given and is related to the expected level of infrared signals from glucose in humans.

Spectral reflectance "deconstruction" of the Murchison CM2 carbonaceous chondrite and implications for spectroscopic investigations of dark asteroids

NASA Astrophysics Data System (ADS)

Cloutis, Edward A.; Pietrasz, Valerie B.; Kiddell, Cain; Izawa, Matthew R. M.; Vernazza, Pierre; Burbine, Thomas H.; DeMeo, Francesca; Tait, Kimberly T.; Bell, James F.; Mann, Paul; Applin, Daniel M.; Reddy, Vishnu

2018-05-01

Carbonaceous chondrites (CCs) are important materials for understanding the early evolution of the solar system and delivery of volatiles and organic material to the early Earth. Presumed CC-like asteroids are also the targets of two current sample return missions: OSIRIS-REx to asteroid Bennu and Hayabusa-2 to asteroid Ryugu, and the Dawn orbital mission at asteroid Ceres. To improve our ability to identify and characterize CM2 CC-type parent bodies, we have examined how factors such as particle size, particle packing, and viewing geometry affect reflectance spectra of the Murchison CM2 CC. The derived relationships have implications for disc-resolved examinations of dark asteroids and sampleability. It has been found that reflectance spectra of slabs are more blue-sloped (reflectance decreasing toward longer wavelengths as measured by the 1.8/0.6 μm reflectance ratio), and generally darker, than powdered sample spectra. Decreasing the maximum grain size of a powdered sample results in progressively brighter and more red-sloped spectra. Decreasing the average grain size of a powdered sample results in a decrease in diagnostic absorption band depths, and redder and brighter spectra. Decreasing porosity of powders and variations in surface texture result in spectral changes that may be different as a function of viewing geometry. Increasing thickness of loose dust on a denser powdered substrate leads to a decrease in absorption band depths. Changes in viewing geometry lead to different changes in spectral metrics depending on whether the spectra are acquired in backscatter or forward-scatter geometries. In backscattered geometry, increasing phase angle leads to an initial increase and then decrease in spectral slope, and a general decrease in visible region reflectance and absorption band depths, and frequent decreases in absorption band minima positions. In forward scattering geometry, increasing phase angle leads to small non-systematic changes in spectral slope, and general decreases in visible region reflectance, and absorption band depths. The highest albedos and larger band depths are generally seen in the lowest phase angle backscattering geometry spectra. The reddest spectra are generally seen in the lowest phase angle backscatter geometry spectra. For the same phase angle, spectra acquired in forward scatter geometry are generally redder and darker and have shallower absorption bands than those acquired in backscatter geometry. Overall, backscatter geometry-acquired spectra are flatter, brighter, and have deeper 0.7 μm region absorption band depths than forward scatter geometry-acquired spectra. It was also found that the 0.7, 0.9, and 1.1 μm absorption bands in Murchison spectra, which are attributable to various Fe electronic processes, are ubiquitous and can be used to recognize CM2 chondrites regardless of the physical properties of the meteorite and viewing geometry.

Spectromicroscopy of boron in human glioblastomas following administration of Na2B12H11SH.

PubMed

Gilbert, B; Perfetti, L; Fauchoux, O; Redondo, J; Baudat, P A; Andres, R; Neumann, M; Steen, S; Gabel, D; Mercanti, D; Ciotti, M T; Perfetti, P; Margaritondo, G; De Stasio, G

2000-07-01

Boron neutron capture therapy (BNCT) is an experimental, binary treatment for brain cancer which requires as the first step that tumor tissue is targeted with a boron-10 containing compound. Subsequent exposure to a thermal neutron flux results in destructive, short range nuclear reaction within 10 microm of the boron compound. The success of the therapy requires than the BNCT agents be well localized in tumor, rather than healthy tissue. The MEPHISTO spectromicroscope, which performs microchemical analysis by x-ray absorption near edge structure (XANES) spectroscopy from microscopic areas, has been used to study the distribution of trace quantities of boron in human brain cancer tissues surgically removed from patients first administered with the compound Na2B12H11SH (BSH). The interpretation of XANES spectra is complicated by interference from physiologically present sulfur and phosphorus, which contribute structure in the same energy range as boron. We addressed this problem with the present extensive set of spectra from S, B, and P in relevant compounds. We demonstrate that a linear combination of sulfate, phosphate and BSH XANES can be used to reproduce the spectra acquired on boron-treated human brain tumor tissues. We analyzed human glioblastoma tissue from two patients administered and one not administered with BSH. As well as weak signals attributed to BSH, x-ray absorption spectra acquired from tissue samples detected boron in a reduced chemical state with respect to boron in BSH. This chemical state was characterized by a sharp absorption peak at 188.3 eV. Complementary studies on BSH reference samples were not able to reproduce this chemical state of boron, indicating that it is not an artifact produced during sample preparation or x-ray exposure. These data demonstrate that the chemical state of BSH may be altered by in vivo metabolism.

Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1991-08-01

The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye

2015-09-17

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

Equilibrium Structures and Absorption Spectra for SixOy-nH2O Molecular Clusters using Density Functional Theory

DTIC Science & Technology

2017-05-04

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9723 Equilibrium Structures and Absorption Spectra for SixOy-nH2O Molecular...Absorption Spectra for SixOy-nH2O Molecular Clusters using Density Functional Theory L. Huang, S.G. Lambrakos, and L. Massa1 Naval Research Laboratory, Code...and time-dependent density functional theory (TD-DFT). The size of the clusters considered is relatively large compared to those considered in

Soft x-ray absorption spectra of ilmenite family.

PubMed

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

2001-03-01

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

UV laser photoactivation of hexachloroplatinate bound to individual nucleobases in vacuo as molecular level probes of a model photopharmaceutical.

PubMed

Matthews, Edward; Sen, Ananya; Yoshikawa, Naruo; Bergström, Ed; Dessent, Caroline E H

2016-06-01

Isolated molecular clusters of adenine, cytosine, thymine and uracil bound to hexachloroplatinate, PtCl6(2-), have been studied using laser electronic photodissociation spectroscopy to investigate photoactivation of a platinum complex in the vicinity of a nucleobase. These metal complex-nucleobase clusters represent model systems for identifying the fundamental photochemical processes occurring in photodynamic platinum drug therapies that target DNA. This is the first study to explore the specific role of a strongly photoactive platinum compound in the aggregate complex. Each of the clusters studied displays a broadly similar absorption spectra, with a strong λmax ∼ 4.6 eV absorption band and a subsequent increase in the absorption intensity towards higher spectral-energy. The absorption bands are traced to ligand-to-metal-charge-transfer excitations on the PtCl6(2-) moiety within the cluster, and result in Cl(-)·nucleobase and PtCl5(-) as primary photofragments. These results demonstrate how selective photoexcitation can drive distinctive photodecay channels for a model photo-pharmaceutical. In addition, cluster absorption due to excitation of nucleobase-centred chromophores is observed in the region around 5 eV. For the uracil cluster, photofragments consistent with ultrafast decay of the excited state and vibrational predissociation on the ground-state surface are observed. However, this decay channel becomes successively weaker on going from thymine to cytosine to adenine, due to differential coupling of the excited states to the electron detachment continuum. These effects demonstrate the distinctive photophysical characteristics of the different nucleobases, and are discussed in the context of the recently recorded photoelectron spectra of theses clusters.

Growth and laser properties of Yb : Ca 4YO(BO 3) 3 crystal

NASA Astrophysics Data System (ADS)

Zhang, Huaijin; Meng, Xianlin; Zhu, Li; Wang, Pu; Liu, Xuesong; Cheng, Ruiping; Dawes, Judith; Dekker, Peter; Zhang, Shaojun; Sun, Lianke

1999-04-01

Yb : Ca 4YO(BO 3) 3 (Yb : YCOB) crystal has been grown by the Czochralski method. The absorption and fluorescence spectra have been measured. The green luminescence is also observed. The output laser at 1032 nm has been demonstrated pumped by laser diode (LD) at 976.4 nm.

Targeting Inaccurate Atomic Data in the Eta Car Ejecta Absorption

NASA Technical Reports Server (NTRS)

Nielsen, K. E.; Kober, G. Vieira; Gull, T. R.; Blackwell-Whitehead, R.; Nilsson, H.

2006-01-01

The input from the laboratory spectroscopist community has on many occasions helped the analysis of the eta Car spectrum. Our analysis has targeted spectra where improved wavelengths and oscillator strengths are needed. We will demonstrate how experimentally derived atomic data have improved our spectral analysis, and illuminate where more work still is needed.

Time-dependent nonequilibrium soft x-ray response during a spin crossover

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Veenendaal, Michel

The rapid development of high-brilliance pulsed X-ray sources with femtosecond time resolution has created a need for a better theoretical understanding of the time-dependent soft-X-ray response of dissipative many-body quantum systems. It is demonstrated how soft-X-ray spectroscopies, such as X-ray absorption and resonant inelastic X-ray scattering at transition-metal L-edges, can provide insight into intersystem crossings, such as a spin crossover. The photoinduced doublet-to-quartet spin crossover on cobalt in Fe-Co Prussian blue analogues is used as an example to demonstrate how the X-ray response is affected by the dissipative nonequilibrium dynamics. The time-dependent soft-X-ray spectra provide a wealth of information thatmore » reflect the changes in the nonequilibrium initial state via continuously changing spectral lineshapes that cannot be decomposed into initial photoexcited and final metastable spectra, strong broadenings, a collapse of clear selection rules during the intersystem crossing, strong fluctuations in the isotropic branching ratio in X-ray absorption, and crystal-field collapse/oscillations and strongly time-dependent anti-Stokes processes in RIXS.« less

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

NASA Astrophysics Data System (ADS)

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

2007-04-01

An optimization method of smoothing noisy spectra was developed to investigate faint absorption bands in the visual spectral region of reflectance spectra of asteroids and the compositional information derived from their analysis. The smoothing algorithm is called "optimal" because the algorithm determines the best running box size to separate weak absorption bands from the noise. The method is tested for its sensitivity to identifying false features in the smoothed spectrum, and its correctness of forecasting real absorption bands was tested with artificial spectra simulating asteroid reflectance spectra. After validating the method we optimally smoothed 22 vestoid spectra from SMASS1 [Xu, Sh., Binzel, R.P., Burbine, T.H., Bus, S.J., 1995. Icarus 115, 1-35]. We show that the resulting bands are not telluric features. Interpretation of the absorption bands in the asteroid spectra was based on the spectral properties of both terrestrial and meteorite pyroxenes. The bands located near 480, 505, 530, and 550 nm we assigned to spin-forbidden crystal field bands of ferrous iron, whereas the bands near 570, 600, and 650 nm are attributed to the crystal field bands of trivalent chromium and/or ferric iron in low-calcium pyroxenes on the asteroids' surface. While not measured by microprobe analysis, Fe 3+ site occupancy can be measured with Mössbauer spectroscopy, and is seen in trace amounts in pyroxenes. We believe that trace amounts of Fe 3+ on vestoid surfaces may be due to oxidation from impacts by icy bodies. If that is the case, they should be ubiquitous in the asteroid belt wherever pyroxene absorptions are found. Pyroxene composition of four asteroids of our set is determined from the band position of absorptions at 505 and 1000 nm, implying that there can be orthopyroxenes in all range of ferruginosity on the vestoid surfaces. For the present we cannot unambiguously interpret of the faint absorption bands that are seen in the spectra of 4005 Dyagilev, 4038 Kristina, 4147 Lennon, and 5143 Heracles. Probably there are other spectrally active materials along with pyroxenes on the surfaces of these asteroids.

DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

PubMed

Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

2013-01-01

Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2).

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

PubMed

Grante, Ilze; Actins, Andris; Orola, Liana

2014-08-14

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

A search for formic acid in the upper troposphere - A tentative identification of the 1105-per cm nu-6 band Q branch in high-resolution balloon-borne solar absorption spectra

NASA Technical Reports Server (NTRS)

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

1984-01-01

Infrared solar absorption spectra recorded at 0.02-per cm resolution during a balloon flight from Alamogordo, NM (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105 per cm has been tentatively identified in upper tropospheric spectra as due to the nu-6 band Q branch. A preliminary analysis indicates a concentration of about 0.6 ppbv and 0.4 ppbv near 8 and 10 km, respectively.

Substituent and solvent effects on the UV/vis absorption spectra of 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones

NASA Astrophysics Data System (ADS)

Mijin, Dušan Ž.; Ušćumlić, Gordana S.; Perišić-Janjić, Nada U.; Valentić, Nataša V.

2006-01-01

Absorption spectra of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones have been recorded in 12 protic and aprotic solvents in the range 200-600 nm. The effects of substituents on the absorption spectra of these new azo dyes are interpreted by correlation of absorption frequencies with Hammett equation. The solute-solvent interactions were clarified on the basis of linear solvation energy relationships concept proposed by Kamlet and Taft. The 2-pyridone/2-hydroxypiridine tautomeric equilibration is found to depend upon substituents as well as on solvents.

The absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphthalenes in crystalline matrixes at 77 K

NASA Astrophysics Data System (ADS)

Iliescu, T.; Milea, I.; Abdolrahman, P. M.

1984-03-01

The paper studies the absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphtalenes (α, β-F, Cl,BrN) in different matrixes at 77 K and different concentrations. From these spectra one obtaines the vibrational frequences.

Use of a Si(Li) detector as β spectrometer.

PubMed

Dryák, P; Kovář, P

2014-05-01

The aim of this work is to demonstrate the capability of a Si(Li) detector for the measurement of β spectra, despite the energy absorption in air and in the Be window. A simple source holder fixes the source on the symmetry axis at 3mm from the detector window. The β-sources are produced by evaporation on a plastic backing plate. Absorbing materials between the source and the sensitive volume of the detector are 3 mm of air, a Be window, 0.1 μm Si and 20 nm of gold. A model of the detector was created for β spectra simulation using the MCNP 4A code. Experimental spectra of (14)C, (147)Pm, (204)Tl, (90)Sr/(90)Y were compared with simulated spectra. © 2013 Published by Elsevier Ltd.

Luminescent hyperbolic metasurfaces

NASA Astrophysics Data System (ADS)

Smalley, J. S. T.; Vallini, F.; Montoya, S. A.; Ferrari, L.; Shahin, S.; Riley, C. T.; Kanté, B.; Fullerton, E. E.; Liu, Z.; Fainman, Y.

2017-01-01

When engineered on scales much smaller than the operating wavelength, metal-semiconductor nanostructures exhibit properties unobtainable in nature. Namely, a uniaxial optical metamaterial described by a hyperbolic dispersion relation can simultaneously behave as a reflective metal and an absorptive or emissive semiconductor for electromagnetic waves with orthogonal linear polarization states. Using an unconventional multilayer architecture, we demonstrate luminescent hyperbolic metasurfaces, wherein distributed semiconducting quantum wells display extreme absorption and emission polarization anisotropy. Through normally incident micro-photoluminescence measurements, we observe absorption anisotropies greater than a factor of 10 and degree-of-linear polarization of emission >0.9. We observe the modification of emission spectra and, by incorporating wavelength-scale gratings, show a controlled reduction of polarization anisotropy. We verify hyperbolic dispersion with numerical simulations that model the metasurface as a composite nanoscale structure and according to the effective medium approximation. Finally, we experimentally demonstrate >350% emission intensity enhancement relative to the bare semiconducting quantum wells.

Terahertz spectroscopic investigation of human gastric normal and tumor tissues

NASA Astrophysics Data System (ADS)

Hou, Dibo; Li, Xian; Cai, Jinhui; Ma, Yehao; Kang, Xusheng; Huang, Pingjie; Zhang, Guangxin

2014-09-01

Human dehydrated normal and cancerous gastric tissues were measured using transmission time-domain terahertz spectroscopy. Based on the obtained terahertz absorption spectra, the contrasts between the two kinds of tissue were investigated and techniques for automatic identification of cancerous tissue were studied. Distinctive differences were demonstrated in both the shape and amplitude of the absorption spectra between normal and tumor tissue. Additionally, some spectral features in the range of 0.2~0.5 THz and 1~1.5 THz were revealed for all cancerous gastric tissues. To systematically achieve the identification of gastric cancer, principal component analysis combined with t-test was used to extract valuable information indicating the best distinction between the two types. Two clustering approaches, K-means and support vector machine (SVM), were then performed to classify the processed terahertz data into normal and cancerous groups. SVM presented a satisfactory result with less false classification cases. The results of this study implicate the potential of the terahertz technique to detect gastric cancer. The applied data analysis methodology provides a suggestion for automatic discrimination of terahertz spectra in other applications.

On the magnetic circular dichroism of benzene. A density-functional study

NASA Astrophysics Data System (ADS)

Kaminský, Jakub; Kříž, Jan; Bouř, Petr

2017-04-01

Spectroscopy of magnetic circular dichroism (MCD) provides enhanced information on molecular structure and a more reliable assignment of spectral bands than absorption alone. Theoretical modeling can significantly enhance the information obtained from experimental spectra. In the present study, the time dependent density functional theory is employed to model the lowest-energy benzene transitions, in particular to investigate the role of the Rydberg states and vibrational interference in spectral intensities. The effect of solvent is explored on model benzene-methane clusters. For the lowest-energy excitation, the vibrational sub-structure of absorption and MCD spectra is modeled within the harmonic approximation, providing a very good agreement with the experiment. The simulations demonstrate that the Rydberg states have a much stronger effect on the MCD intensities than on the absorption, and a very diffuse basis set must be used to obtain reliable results. The modeling also indicates that the Rydberg-like states and associated transitions may persist in solutions. Continuum-like solvent models are thus not suitable for their modeling; solvent-solute clusters appear to be more appropriate, providing they are large enough.

Soft X-Ray Absorption Spectroscopy of High-Abrasion-Furnace Carbon Black

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muramatsu, Yasuji; Harada, Ryusuke; Gullikson, Eric M.

2007-02-02

The soft x-ray absorption spectra of high-abrasion-furnace carbon black were measured to obtain local-structure/chemical-states information of the primary particles and/or crystallites. The soft x-ray absorption spectral features of carbon black represent broader {pi}* and {sigma}* peak structures compared to highly oriented pyrolytic graphite (HOPG). The subtracted spectra between the carbon black and HOPG, (carbon black) - (HOPG), show double-peak structures on both sides of the {pi}* peak. The lower-energy peak, denoted as the 'pre-peak', in the subtracted spectra and the {pi}*/{sigma}* peak intensity ratio in the absorption spectra clearly depend on the specific surface area by nitrogen adsorption (NSA). Therefore,more » it is concluded that the pre-peak intensity and the {pi}*/{sigma}* ratio reflect the local graphitic structure of carbon black.« less

The effect of annulation of benzene rings on the photophysics and electronic structure of tetraazachlorin molecules

NASA Astrophysics Data System (ADS)

Pershukevich, P. P.; Volkovich, D. I.; Gladkov, L. L.; Dudkin, S. V.; Kuzmitsky, V. A.; Makarova, E. A.; Solovyev, K. N.

2017-10-01

The photophysics and electronic structure of tribenzotetraazachlorins (H2, Zn, and Mg), which are novel analogues of phtalocyanines, have been studied experimentally and theoretically. At 293 K, the electronic absorption, fluorescence, and fluorescence excitation spectra are recorded and the fluorescence quantum yield and lifetime, as well as the quantum yield of singlet oxygen generation, are measured; at 77 K, the fluorescence, fluorescence excitation, and fluorescence polarization spectra are recorded and the fluorescence lifetime values are measured. The dependences of the absorption spectra and photophysical parameters on the structure variation are analyzed in detail. Quantum-chemical calculations of the electronic structure and absorption spectra of tribenzotetraazachlorins (H2, Mg) are performed using the INDO/Sm method (modified INDO/S method) based on molecular-geometry optimization by the DFT PBE/TZVP method. The results of quantum-chemical calculations of the electronic absorption spectra are in very good agreement with the experimental data for the transitions to two lower electronic states.

Broadband and wide angle near-unity absorption in graphene-insulator-metal thin film stacks

NASA Astrophysics Data System (ADS)

Zhang, H. J.; Zheng, G. G.; Chen, Y. Y.; Xu, L. H.

2018-05-01

Broadband unity absorption in graphene-insulator-metal (GIM) structures is demonstrated in the visible (VIS) and near-infrared (NIR) spectra. The spectral characteristics possess broadband absorption peaks, by simply choosing a stack of GIM, while no nanofabrication steps and patterning are required, and thus can be easily fabricated to cover a large area. The electromagnetic (EM) waves can be entirely trapped and the absorption can be greatly enhanced are verified with the finite-difference time-domain (FDTD) and rigorous coupled wave analysis (RCWA) methods. The position and the number of the absorption peak can be totally controlled by adjusting the thickness of the insulator layer. The proposed absorber maintains high absorption (above 90%) for both transverse electric (TE) and transverse magnetic (TM) polarizations, and for angles of incidence up to 80°. This work opens up a promising approach to realize perfect absorption (PA) with ultra-thin film, which could implicate many potential applications in optical detection and optoelectronic devices.

Electrically-induced polarization selection rules of a graphene quantum dot

NASA Astrophysics Data System (ADS)

Dong, Qing-Rui; Li, Yan; Jia, Chen; Wang, Fu-Li; Zhang, Ya-Ting; Liu, Chun-Xiang

2018-05-01

We study theoretically the single-electron triangular zigzag graphene quantum dot in uniform in-plane electric fields. The absorption spectra of the dot are calculated by the tight-binding method. The energy spectra and the distribution of wave functions are also presented to analyse the absorption spectra. The orthogonal zero-energy eigenstates are arranged along to the direction of the external field. The remarkable result is that all intraband transitions and some interband transitions are forbidden when the absorbed light is polarized along the direction of the electric field. With x-direction electric field, all intraband absorption is y polarized due to the electric-field-direction-polarization selection rule. Moreover, with y-direction electric field, all absorption is either x or y polarized due to the parity selection rule as well as to the electric-field-direction-polarization selection rule. Our calculation shows that the formation of the absorption spectra is co-decided by the polarization selection rules and the overlap between the eigenstates of the transition.

White light photothermal lens spectrophotometer for the determination of absorption in scattering samples.

PubMed

Marcano, Aristides; Alvarado, Salvador; Meng, Junwei; Caballero, Daniel; Moares, Ernesto Marín; Edziah, Raymond

2014-01-01

We developed a pump-probe photothermal lens spectrophotometer that uses a broadband arc-lamp and a set of interference filters to provide tunable, nearly monochromatic radiation between 370 and 730 nm as the pump light source. This light is focused onto an absorbing sample, generating a photothermal lens of millimeter dimensions. A highly collimated monochromatic probe light from a low-power He-Ne laser interrogates the generated lens, yielding a photothermal signal proportional to the absorption of light. We measure the absorption spectra of scattering dye solutions using the device. We show that the spectra are not affected by the presence of scattering, confirming that the method only measures the absorption of light that results in generation of heat. By comparing the photothermal spectra with the usual absorption spectra determined using commercial transmission spectrophotometers, we estimate the quantum yield of scattering of the sample. We discuss applications of the device for spectroscopic characterization of samples such as blood and gold nanoparticles that exhibit a complex behavior upon interaction with light.

Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

PubMed Central

Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

2016-01-01

The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup. PMID:26698072

Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution.

PubMed

Müller, Oliver; Nachtegaal, Maarten; Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald

2016-01-01

The quick-EXAFS (QEXAFS) method adds time resolution to X-ray absorption spectroscopy (XAS) and allows dynamic structural changes to be followed. A completely new QEXAFS setup consisting of monochromator, detectors and data acquisition system is presented, as installed at the SuperXAS bending-magnet beamline at the Swiss Light Source (Paul Scherrer Institute, Switzerland). The monochromator uses Si(111) and Si(311) channel-cut crystals mounted on one crystal stage, and remote exchange allows an energy range from 4.0 keV to 32 keV to be covered. The spectral scan range can be electronically adjusted up to several keV to cover multiple absorption edges in one scan. The determination of the Bragg angle close to the position of the crystals allows high-accuracy measurements. Absorption spectra can be acquired with fast gridded ionization chambers at oscillation frequencies of up to 50 Hz resulting in a time resolution of 10 ms, using both scan directions of each oscillation period. The carefully developed low-noise detector system yields high-quality absorption data. The unique setup allows both state-of-the-art QEXAFS and stable step-scan operation without the need to exchange whole monochromators. The long-term stability of the Bragg angle was investigated and absorption spectra of reference materials as well as of a fast chemical reaction demonstrate the overall capabilities of the new setup.

Data Processing Algorithm for Diagnostics of Combustion Using Diode Laser Absorption Spectrometry.

PubMed

Mironenko, Vladimir R; Kuritsyn, Yuril A; Liger, Vladimir V; Bolshov, Mikhail A

2018-02-01

A new algorithm for the evaluation of the integral line intensity for inferring the correct value for the temperature of a hot zone in the diagnostic of combustion by absorption spectroscopy with diode lasers is proposed. The algorithm is based not on the fitting of the baseline (BL) but on the expansion of the experimental and simulated spectra in a series of orthogonal polynomials, subtracting of the first three components of the expansion from both the experimental and simulated spectra, and fitting the spectra thus modified. The algorithm is tested in the numerical experiment by the simulation of the absorption spectra using a spectroscopic database, the addition of white noise, and the parabolic BL. Such constructed absorption spectra are treated as experimental in further calculations. The theoretical absorption spectra were simulated with the parameters (temperature, total pressure, concentration of water vapor) close to the parameters used for simulation of the experimental data. Then, spectra were expanded in the series of orthogonal polynomials and first components were subtracted from both spectra. The value of the correct integral line intensities and hence the correct temperature evaluation were obtained by fitting of the thus modified experimental and simulated spectra. The dependence of the mean and standard deviation of the evaluation of the integral line intensity on the linewidth and the number of subtracted components (first two or three) were examined. The proposed algorithm provides a correct estimation of temperature with standard deviation better than 60 K (for T = 1000 K) for the line half-width up to 0.6 cm -1 . The proposed algorithm allows for obtaining the parameters of a hot zone without the fitting of usually unknown BL.

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

NASA Technical Reports Server (NTRS)

Sherman, D. M.

1985-01-01

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

Influence of dose on particle size and optical properties of colloidal platinum nanoparticles.

PubMed

Gharibshahi, Elham; Saion, Elias

2012-11-12

Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size.

Influence of Dose on Particle Size and Optical Properties of Colloidal Platinum Nanoparticles

PubMed Central

Gharibshahi, Elham; Saion, Elias

2012-01-01

Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size. PMID:23203091

Laboratory absorption spectra of molecules at interstellar cloud temperatures - First measurements on CO at about 97 nm

NASA Technical Reports Server (NTRS)

Smith, P. L.; Yoshino, K.; Stark, G.; Ito, K.; Stevens, M. H.

1991-01-01

In the 91-100 nm spectral region, where absorption of photons by interstellar CO usually leads to dissociation, laboratory spectra obtained at 295 K show that most CO bands are both overlapped and perturbed. Reliable band oscillator strengths cannot be extracted from such spectra. As a consequence, synthetic extreme-ultraviolet absorption spectra for CO at the low temperatures that prevail in interstellar clouds are uncertain. A supersonic expansion technique has been used to cool CO to 30 K and three bands in the 97-nm region have been studied with high spectral resolution. The measured spectrum at 30 K is in reasonable agreement with some published modeled spectra, but the ratios of integrated cross sections are somewhat different from those determined from low resolution spectra obtained at 295 K, in which the bands are blended.

Sub-Terrahertz Spectroscopy of E.COLI Dna: Experiment, Statistical Model, and MD Simulations

NASA Astrophysics Data System (ADS)

Sizov, I.; Dorofeeva, T.; Khromova, T.; Gelmont, B.; Globus, T.

2012-06-01

We will present result of combined experimental and computational study of sub-THz absorption spectra from Escherichia coli (E.coli) DNA. Measurements were conducted using a Bruker FTIR spectrometer with a liquid helium cooled bolometer and a recently developed frequency domain sensor operating at room temperature, with spectral resolution of 0.25 cm-1 and 0.03 cm-1, correspondingly. We have earlier demonstrated that molecular dynamics (MD) simulation can be effectively applied for characterizing relatively small biological molecules, such as transfer RNA or small protein thioredoxin from E. coli , and help to understand and predict their absorption spectra. Large size of DNA macromolecules ( 5 million base pairs for E. coli DNA) prevents, however, direct application of MD simulation at the current level of computational capabilities. Therefore, by applying a second order Markov chain approach and Monte-Carlo technique, we have developed a new statistical model to construct DNA sequences from biological cells. These short representative sequences (20-60 base pairs) are built upon the most frequently repeated fragments (2-10 base pairs) in the original DNA. Using this new approach, we constructed DNA sequences for several non-pathogenic strains of E.coli, including a well-known strain BL21, uro-pathogenic strain, CFT073, and deadly EDL933 strain (O157:H7), and used MD simulations to calculate vibrational absorption spectra of these strains. Significant differences are clearly present in spectra of strains in averaged spectra and in all components for particular orientations. The mechanism of interaction of THz radiation with a biological molecule is studied by analyzing dynamics of atoms and correlation of local vibrations in the modeled molecule. Simulated THz vibrational spectra of DNA are compared with experimental results. With the spectral resolution of 0.1 cm-1 or better, which is now available in experiments, the very easy discrimination between different strains of the same bacteria becomes possible.

Quantitative comparison of the absorption spectra of the gas mixtures in analogy to the criterion of Pearson

NASA Astrophysics Data System (ADS)

Kistenev, Yu. V.; Kuzmin, D. A.; Sandykova, E. A.; Shapovalov, A. V.

2015-11-01

An approach to the reduction of the space of the absorption spectra, based on the original criterion for profile analysis of the spectra, was proposed. This criterion dates back to the known statistics chi-square test of Pearson. Introduced criterion allows to quantify the differences of spectral curves.

Detection and identification of illicit drugs using terahertz imaging

NASA Astrophysics Data System (ADS)

Lu, Meihong; Shen, Jingling; Li, Ning; Zhang, Yan; Zhang, Cunlin; Liang, Laishun; Xu, Xiaoyu

2006-11-01

We demonstrated an advanced terahertz imaging technique for detection and identification of illicit drugs by introducing the component spatial pattern analysis. As an explanation, the characteristic fingerprint spectra and refractive index of ketamine were first measured with terahertz time-domain spectroscopy both in the air and nitrogen. The results obtained in the ambient air indicated that some absorption peaks are not obvious or probably not dependable. It is necessary and important to present a more practical technique for the detection. The spatial distributions of several illicit drugs [3,4-methylenedioxymethamphetamine, methylenedioxyamphetamine, heroin, acetylcodeine, morphine, and ketamine], widely consumed in the world, were obtained from terahertz images using absorption spectra previously measured in the range from 0.2to2.6THz in the ambient air. The different kinds of pure illicit drugs hidden in mail envelopes were inspected and identified. It could be an effective method in the field of safety inspection.

Visual pigment spectra of the comma butterfly, Polygonia c-album, derived from in vivo epi-illumination microspectrophotometry.

PubMed

Vanhoutte, Kurt J A; Stavenga, Doekele G

2005-05-01

The visual pigments in the compound eye of the comma butterfly, Polygonia c-album, were investigated in a specially designed epi-illumination microspectrophotometer. Absorption changes due to photochemical conversions of the visual pigments, or due to light-independent visual pigment decay and regeneration, were studied by measuring the eye shine, i.e., the light reflected from the tapetum located in each ommatidium proximal to the visual pigment-bearing rhabdom. The obtained absorbance difference spectra demonstrated the dominant presence of a green visual pigment. The rhodopsin and its metarhodopsin have absorption peak wavelengths at 532 nm and 492 nm, respectively. The metarhodopsin is removed from the rhabdom with a time constant of 15 min and the rhodopsin is regenerated with a time constant of 59 min (room temperature). A UV rhodopsin with metarhodopsin absorbing maximally at 467 nm was revealed, and evidence for a blue rhodopsin was obtained indirectly.

The P K-near edge absorption spectra of phosphates

NASA Astrophysics Data System (ADS)

Franke, R.; Hormes, J.

1995-12-01

The X-ray absorption near edge structure (XANES) at the P K-edge in several orthophosphates with various cations, in condensed, and in substituted sodium phosphates have been measured using synchrotron radiation from the ELSA storage ring at the University of Bonn. The measured spectra demonstrate that chemical changes beyond the PO 4- tetrahedra are reflected by energy shifts of the pre-edge and continuum resonances, by the presence of characteristic shoulders and new peaks and by differences in the intensity of the white line. We discuss the energy differences between the white line positions and the corresponding P ls binding energies as a measure of half of the energy gap. The corresponding values correlate with the valence of the cations and the intensity of the white lines. The energy positions of the continuum resonances are discussed on the basis of an empirical bond-length correlation supporting a 1/ r2 - dependence.

Synthesis, structural characterization and tautomeric properties of some novel bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Safarnejad, Mastaneh

Nine new bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone have been synthesized in two steps using Knoevenagel condensation and diazotization-coupling reaction. The structures of the compounds were confirmed by UV-vis, IR, 1H NMR and 13C NMR spectroscopic techniques. The spectral characterizations demonstrate that there is an equilibrium between the azo (T1) and hydrazine (T2 and T3) tautomers for all prepared dyes in solutions. In addition, the solvatochromic behavior of the prepared dyes was evaluated using polarity/polarizability parameter (π*) in various solvents. The UV-vis absorption spectra of dyes show a bathochromic shift with increasing polarity and base strength of the solvents. Finally, the effects of acid and base on the UV-vis absorption spectra of the dyes with different substituent in diazo component are reported.

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.

Wavelength-selective mid-infrared metamaterial absorbers with multiple tungsten cross resonators.

PubMed

Li, Zhigang; Stan, Liliana; Czaplewski, David A; Yang, Xiaodong; Gao, Jie

2018-03-05

Wavelength-selective metamaterial absorbers in the mid-infrared range are demonstrated by using multiple tungsten cross resonators. By adjusting the geometrical parameters of cross resonators in single-sized unit cells, near-perfect absorption with single absorption peak tunable from 3.5 µm to 5.5 µm is realized. The combination of two, three, or four cross resonators of different sizes in one unit cell enables broadband near-perfect absorption at mid-infrared range. The obtained absorption spectra exhibit omnidirectionality and weak dependence on incident polarization. The underlying mechanism of near-perfect absorption with cross resonators is further explained by the optical mode analysis, dispersion relation and equivalent RLC circuit model. Moreover, thermal analysis is performed to study the heat generation and temperature increase in the cross resonator absorbers, while the energy conversion efficiency is calculated for the thermophotovoltaic system made of the cross resonator thermal emitters and low-bandgap semiconductors.

Hyperpolarized 13C pyruvate mouse brain metabolism with absorptive-mode EPSI at 1 T

NASA Astrophysics Data System (ADS)

Miloushev, Vesselin Z.; Di Gialleonardo, Valentina; Salamanca-Cardona, Lucia; Correa, Fabian; Granlund, Kristin L.; Keshari, Kayvan R.

2017-02-01

The expected signal in echo-planar spectroscopic imaging experiments was explicitly modeled jointly in spatial and spectral dimensions. Using this as a basis, absorptive-mode type detection can be achieved by appropriate choice of spectral delays and post-processing techniques. We discuss the effects of gradient imperfections and demonstrate the implementation of this sequence at low field (1.05 T), with application to hyperpolarized [1-13C] pyruvate imaging of the mouse brain. The sequence achieves sufficient signal-to-noise to monitor the conversion of hyperpolarized [1-13C] pyruvate to lactate in the mouse brain. Hyperpolarized pyruvate imaging of mouse brain metabolism using an absorptive-mode EPSI sequence can be applied to more sophisticated murine disease and treatment models. The simple modifications presented in this work, which permit absorptive-mode detection, are directly translatable to human clinical imaging and generate improved absorptive-mode spectra without the need for refocusing pulses.

Force-detected nanoscale absorption spectroscopy in water at room temperature using an optical trap

NASA Astrophysics Data System (ADS)

Parobek, Alexander; Black, Jacob W.; Kamenetska, Maria; Ganim, Ziad

2018-04-01

Measuring absorption spectra of single molecules presents a fundamental challenge for standard transmission-based instruments because of the inherently low signal relative to the large background of the excitation source. Here we demonstrate a new approach for performing absorption spectroscopy in solution using a force measurement to read out optical excitation at the nanoscale. The photoinduced force between model chromophores and an optically trapped gold nanoshell has been measured in water at room temperature. This photoinduced force is characterized as a function of wavelength to yield the force spectrum, which is shown to be correlated to the absorption spectrum for four model systems. The instrument constructed for these measurements combines an optical tweezer with frequency domain absorption spectroscopy over the 400-800 nm range. These measurements provide proof-of-principle experiments for force-detected nanoscale spectroscopies that operate under ambient chemical conditions.

Vectorial photoinduced energy transfer between boron-dipyrromethene (Bodipy) chromophores across a fluorene bridge.

PubMed

Puntoriero, Fausto; Nastasi, Francesco; Campagna, Sebastiano; Bura, Thomas; Ziessel, Raymond

2010-08-02

A series of novel multichromophoric, luminescent compounds has been prepared, and their absorption spectra, luminescence properties (both at 77 K in rigid matrix and at 298 K in fluid solution), and photoinduced intercomponent energy-transfer processes have been studied. The series contains two new multichromophoric systems 1 and 2, each one containing two different boron-dipyrromethene (Bodipy) subunits and one bridging fluorene species, and two fluorene-Bodipy bichromophoric species, 6 and 7. Three monochromophoric compounds, 3, 4, and 5, used as precursors in the synthetic process, were also fully characterized. The absorption spectra of the multichromophoric compounds are roughly the summation of the absorption spectra of their individual components, thus demonstrating the supramolecular nature of the assemblies. Luminescence studies show that quantitative energy transfer occurs in 6 and 7 from the fluorene chromophore to the Bodipy dyes. Luminescence studies, complemented by transient-absorption spectroscopy studies, also indicate that efficient inter-Bodipy energy transfer across the rigid fluorene spacer takes place in 1 and 2, with rate constants, evaluated by several experimental methods, between 2.0 and 7.0 x 10(9) s(-1). Such an inter-Bodipy energy transfer appears to be governed by the Förster mechanism. By taking advantage of the presence of various protonable sites in the substituents of the lower-energy Bodipy subunit of 1 and 2, the effect of protonation on the energy-transfer rates has also been investigated. The results suggest that control of energy-transfer rate and efficiency of inter-Bodipy energy transfer in this type of systems can be achieved by an external, reversible input.

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.

Optical Absorption Spectra of Hydrogenated Microcrystalline Silicon Films by Resonant Photothermal Bending Spectroscopy

NASA Astrophysics Data System (ADS)

Kunii, Toshie; Yoshida, Norimitsu; Hori, Yasuro; Nonomura, Shuichi

2006-05-01

A resonant photothermal bending spectroscopy (PBS) is demonstrated for the measurement of absorption coefficient spectra in hydrogenated microcrystalline silicon (μc-Si:H) and hydrogenated microcrystalline cubic silicon carbide (μc-3C-SiC:H) films. The resonant vibration technique utilized in PBS establishes the sensitivity as α d˜ 5× 10-5 in a vacuum measurement. Appling resonant PBS to μc-Si:H films, a new extra absorption coefficient αex spectrum is observed from 0.6 to 1.2 eV. The αex spectrum has a peak at ˜1.0 eV, and the localized states inducing the αex are located ˜0.35 eV below the conduction band edge of μc-Si:H. A possible explanation for the observed localized state is that an oxidation produces weak bonds at the grain boundaries and/or amorphous silicon tissues. In μc-3C-SiC:H film, an optical band-gap energy of ˜2.2 eV was demonstrated assuming an indirect optical transition. The temperature coefficient of the optical band-gap energy was ˜2.3× 10-4 eV K-1. The αex spectrum of μc-3C-SiC:H film is plateau-shaped and its magnitude is in accord with an increase in grain size.

Optical band gap of thermally deposited Ge-S-Ga thin films

NASA Astrophysics Data System (ADS)

Rana, Anjli; Heera, Pawan; Singh, Bhanu Pratap; Sharma, Raman

2018-05-01

Thin films of Ge20S80-xGax glassy alloy, obtained from melt quenching technique, were deposited on the glass substrate by thermal evaporation technique under a high vacuum conditions (˜ 10-5 Torr). Absorption spectrum fitting method (ASF) is employed to obtain the optical band gap from absorption spectra. This method requires only the measurement of the absorption spectrum of the sample. The width of the band tail was also determined. Optical band gap computed from absorption spectra is found to decrease with an increase in Ga content. The evaluated optical band gap (Eg) is in well agreement with the theoretically predicted Eg and obtained from transmission spectra.

Investigating a physical basis for spectroscopic estimates of leaf nitrogen concentration

USGS Publications Warehouse

Kokaly, R.F.

2001-01-01

The reflectance spectra of dried and ground plant foliage are examined for changes directly due to increasing nitrogen concentration. A broadening of the 2.1-??m absorption feature is observed as nitrogen concentration increases. The broadening is shown to arise from two absorptions at 2.054 ??m and 2.172 ??m. The wavelength positions of these absorptions coincide with the absorption characteristics of the nitrogen-containing amide bonds in proteins. The observed presence of these absorption features in the reflectance spectra of dried foliage is suggested to form a physical basis for high correlations established by stepwise multiple linear regression techniques between the reflectance of dry plant samples and their nitrogen concentration. The consistent change in the 2.1-??m absorption feature as nitrogen increases and the offset position of protein absorptions compared to those of other plant components together indicate that a generally applicable algorithm may be developed for spectroscopic estimates of nitrogen concentration from the reflectance spectra of dried plant foliage samples. ?? 2001 Published by Elsevier Science Ireland Ltd.

Near-infrared spectra of the Martian surface: Reading between the lines

NASA Technical Reports Server (NTRS)

Crisp, D.; Bell, J. F., III

1993-01-01

Moderate-resolution near-infrared (NIR) spectra of Mars have been widely used in studies of the Martian surface because many candidate surface materials have distinctive absorption features at these wavelengths. Recent advances in NIR detector technology and instrumentation have also encouraged studies in this spectral region. The use of moderate spectral resolution has often been justified for NIR surface observations because the spectral features produced by most surface materials are relatively broad, and easily discriminated at this resolution. In spite of this, NIR spectra of Mars are usually very difficult to interpret quantitatively. One problem is that NIR surface absorption features are often only a few percent deep, requiring observations with great signal-to-noise ratios. A more significant problem is that gases in the Martian atmosphere contribute numerous absorption features at these wavelengths. Ground-based observers must also contend with variable absorption by several gases in the Earth's atmosphere (H2O, CO2, O3, N2O, CH4, O2). The strong CO2 bands near 1.4, 1.6, 2.0, 2.7, 4.3, and 4.8 micrometers largely preclude the analysis of surface spectral features at these wavelengths. Martian atmospheric water vapor also contributes significant absorption near 1.33, 1.88, and 2.7 micrometers, but water vapor in the Earth's atmosphere poses a much larger problem to ground-based studies of these spectral regions. The third most important NIR absorber in the Martian atmosphere is CO. This gas absorbs most strongly in the relatively-transparent spectral windows near 4.6 and 2.3 micrometers. It also produces 1-10 percent absorption in the solar spectrum at these NIR wavelengths. This solar CO absorption cannot be adequately removed by dividing the Martian spectrum by that of a star, as is commonly done to calibrate ground-based spectroscopic observations, because most stars do not have identical amounts of CO absorption in their spectra. Here, we describe tow effective methods for eliminating contamination of Martian surface spectra by absorption in the solar, terrestrial, and Martian atmospheres. Both methods involve the use of very-high-resolution spectra that completely resolve the narrow atmospheric absorption lines.

Quantify Glucose Level in Freshly Diabetic's Blood by Terahertz Time-Domain Spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Hua; Chen, Xiaofeng; Ma, Shihua; Wu, Xiumei; Yang, Wenxing; Zhang, Weifeng; Li, Xiao

2018-04-01

We demonstrate the capability of terahertz (THz) time-domain spectroscopy (TDS) to quantify glucose level in ex vivo freshly diabetic's blood. By investigating the THz spectra of different human blood, we find out THz absorption coefficients reflect a high sensitivity to the glucose level in blood. With a quantitative analysis of 70 patients, we demonstrate that the THz absorption coefficients and the blood glucose levels perform a linear relationship. A comparative experiment between THz measurement and glucometers is also conducted with another 20 blood samples, and the results confirm that the relative error is as less as 15%. Our ex vivo human blood study indicates that THz technique has great potential application to diagnose blood glucose level in clinical practice.

The IR Absorption Spectra of Aqueous Solutions of Dimethylsulfoxide over the Frequency Range 50-300 cm-1 and the Mobility of Water Molecules

NASA Astrophysics Data System (ADS)

Klemenkova, Z. S.; Novskova, T. A.; Lyashchenko, A. K.

2008-04-01

The IR absorption spectra of aqueous solutions of dimethylsulfoxide (DMSO) with concentrations from 100% H2O to 100% DMSO were recorded over the frequency range 50-500 cm-1. The absorption spectra were described using the theoretical scheme of hindered rotators. A model was developed according to which orientation relaxation in solution was related to separate rotations of H2O and DMSO molecules through fixed small and (or) large angles in a unified network of H-bonds consisting of several subsystems ordered to various degrees. The calculated absorption spectra were in agreement with the experimental data in the far IR region. Elementary motions of molecules were found to slow down in the passage from pure dimethylsulfoxide to its aqueous solutions. The special features of the hydrophilic and hydrophobic hydration of DMSO polar and nonpolar groups were considered.

Theoretical studies on absorption, emission, and resonance Raman spectra of Coumarin 343 isomers

NASA Astrophysics Data System (ADS)

Wu, Wenpeng; Cao, Zexing; Zhao, Yi

2012-03-01

The vibrationally resolved spectral method and quantum chemical calculations are employed to reveal the structural and spectral properties of Coumarin 343 (C343), an ideal candidate for organic dye photosensitizers, in vacuum and solution. The results manifest that the ground-state energies are dominantly determined by different placements of hydrogen atom in carboxylic group of C343 conformations. Compared to those in vacuum, the electronic absorption spectra in methanol solvent show a hyperchromic property together with the redshift and blueshift for the neutral C343 isomers and their deprotonated anions, respectively. From the absorption, emission, and resonance Raman spectra, it is found that the maximal absorption and emission come from low-frequency modes whereas the high-frequency modes have high Raman activities. The detailed spectra are further analyzed for the identification of the conformers and understanding the potential charge transfer mechanism in their photovoltaic applications.

Solubility of Lead Sulfate in Water and in Sodium Sulfate Solutions: An Experiment in Atomic Absorption Spectrophotometry.

ERIC Educational Resources Information Center

Lehman, Thomas A.; Everett, Wayne W.

1982-01-01

Describes a set of undergraduate laboratory experiments which provide experience in deuteration and derivatization procedures applied to infrared spectroscopy. Basic skills in vacuum-line technique are also taught while measuring infrared spectra of deuterated solid samples and demonstrating the value of derivatization as an aid to interpreting…

LASERS IN MEDICINE: Two-photon excitation of aluminium phthalocyanines

NASA Astrophysics Data System (ADS)

Meshalkin, Yu P.; Alfimov, E. E.; Vasil'ev, N. E.; Denisov, A. N.; Makukha, V. K.; Ogirenko, A. P.

1999-12-01

A demonstration is given of the feasibility of two-photon excitation of aluminium phthalocyanine and of the pharmaceutical preparation 'Fotosens', used in photodynamic therapy. The excitation source was an Nd:YAG laser emitting at the 1064 nm wavelength. The spectra of the two-photon-excited luminescence were obtained and the two-photon absorption cross sections were determined.

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-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

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.

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.

An atlas of ultraviolet spectra of star-forming galaxies

NASA Technical Reports Server (NTRS)

Kinney, A. L.; Bohlin, R. C.; Calzetti, D.; Panagia, N.; Wyse, Rosemary F. G.

1993-01-01

A systematic study is presented of the UV spectra of star-forming galaxies of different morphological type and activity class using a sample drawn from a uniformly reduced IUE data set. The spectra for a wide variety of galaxies, including normal spiral, LINER, starburst, blue compact, blue compact dwarf, and Seyfert 2 galaxies, are presented in the form of spectral energy distributions to demonstrate the overall characteristics according to morphology and activity class and in the form of absolute flux distributions to better show the absorption and emission features of individual objects. The data support the picture based on UV spectra of the Orbiting Astronomical Observatory and of the Astronautical Netherlands Satellite that spiral galaxies of later Hubble class have more flux at the shortest UV wavelengths than do spiral galaxies of earlier Hubble class.

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Studies on the binding behavior of prodigiosin with bovine hemoglobin by multi-spectroscopic techniques

NASA Astrophysics Data System (ADS)

Tang, Jing; Yang, Chao; Zhou, Lin; Ma, Fei; Liu, Shuchao; Wei, Shaohua; Zhou, Jiahong; Zhou, Yanhuai

2012-10-01

In this article, the interaction mechanism of prodigiosin (PG) with bovine hemoglobin (BHb) is studied in detail using various spectroscopic technologies. UV-vis absorption and fluorescence spectra demonstrate the interaction process. The Stern-Volmer plot and the time-resolved fluorescence study suggest the quenching mechanism of fluorescence of BHb by PG is a static quenching procedure, and the hydrophobic interactions play a major role in binding of PG to BHb. Furthermore, synchronous fluorescence studies, Fourier transform infrared (FTIR) and circular dichroism (CD) spectra reveal that the conformation of BHb is changed after conjugation with PG.

Complementary spectroscopic studies of materials of security interest

NASA Astrophysics Data System (ADS)

Burnett, Andrew; Fan, Wenhui; Upadhya, Prashanth; Cunningham, John; Edwards, Howell; Munshi, Tasnim; Hargreaves, Michael; Linfield, Edmund; Davies, Giles

2006-09-01

We demonstrate that, through coherent measurement of the transmitted terahertz frequency electric fields, broadband (0.3 - 8 THz) time-domain spectroscopy can be used to measure far-infrared vibrational modes of a range of drugs-of-abuse and high explosives that are of interest to the forensic and security services. Our results indicate that absorption features in these materials are highly sensitive to the structural and spatial arrangement of the molecules. Terahertz frequency spectra are also compared with high-resolution low-frequency Raman spectra to assist in understanding the low-frequency inter- and intra-molecular vibrational modes of the molecules.

Analysis of drugs-of-abuse and explosives using terahertz time-domain and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Burnett, Andrew; Fan, Wenhui; Upadhya, Prashanth; Cunningham, John; Linfield, Edmund; Davies, Giles; Edwards, Howell; Munshi, Tasnim; O'Neil, Andrew

2006-02-01

We demonstrate that, through coherent measurement of the transmitted terahertz electric fields, broadband (0.3-8THz) time-domain spectroscopy can be used to measure far-infrared vibrational modes of a range of illegal drugs and high explosives that are of interest to the forensic and security services. Our results show that these absorption features are highly sensitive to the structural and spatial arrangement of the molecules. Terahertz frequency spectra are also compared with high-resolution low-frequency Raman spectra to assist in understanding the low frequency inter- and intra-molecular vibrational modes of the molecules.

Terahertz spectral characteristics of two kinds of important functional oligosaccharides

NASA Astrophysics Data System (ADS)

Li, Ge; Liu, Wei; Wang, Wenai

2018-01-01

The absorption spectra of two kinds of important functional oligosaccharides were firstly acquired based on Fourier transform infrared spectroscopy in the range of 0.15-10THz. The simulation results of their infrared spectra were given based on Gaussian software, which were in good agreement with the experiment results. The rotation spectra and some perssad vibration spectra of these molecules were analyzed, and their absorption peaks were exactly identified. The components information was obtained by comparing the simulation results of different molecules.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Transition metal atomic multiplets in the ligand K-edge x-ray absorption spectra and multiple oxidation states in the L2,3 emission of strongly correlated compounds

NASA Astrophysics Data System (ADS)

Jiménez-Mier, J.; Olalde-Velasco, P.; Yang, W.-L.; Denlinger, J.

2014-07-01

We present results that show that atomic multiplet ligand field calculations are in very good agreement with experimental x-ray absorption spectra at the L2,3 edge of transition metal (TM) di-fluorides (MF2, MCrCu). For chromium more than one TM oxidation state is needed to achieve such an agreement. We also show that signature of the TM atomic multiplet can be found at the pre-edge of the fluorine K-edge x-ray absorption spectra. TM atomic multiplet ligand field calculations with a structureless core hole show good agreement with the observed pre-edges in the experimental fluorine absorption spectra. Preliminary results for the comparison between calculated and experimental resonant x-ray emission spectra for nominal CrF2 with more than one oxidation state indicate the presence of three chromium oxidation states in the bulk.

Terahertz Absorption by Cellulose: Application to Ancient Paper Artifacts

NASA Astrophysics Data System (ADS)

Peccianti, M.; Fastampa, R.; Mosca Conte, A.; Pulci, O.; Violante, C.; Łojewska, J.; Clerici, M.; Morandotti, R.; Missori, M.

2017-06-01

Artifacts made of cellulose, such as ancient documents, pose a significant experimental challenge in the terahertz transmission spectra interpretation due to their small optical thickness. In this paper, we describe a method to recover the complex refractive index of cellulose fibers from the terahertz transmission data obtained on single freely standing paper sheets in the (0.2-3.5)-THz range. By using our technique, we eliminate Fabry-Perot effects and recover the absorption coefficient of the cellulose fibers. The obtained terahertz absorption spectra are explained in terms of absorption peaks of the cellulose crystalline phase superimposed to a background contribution due to a disordered hydrogen-bond network. The comparison between the experimental spectra with terahertz vibrational properties simulated by density-functional-theory calculations confirms this interpretation. In addition, evident changes in the terahertz absorption spectra are produced by natural and artificial aging on paper samples, whose final stage is characterized by a spectral profile with only two peaks at about 2.1 and 3.1 THz. These results can be used to provide a quantitative assessment of the state of preservation of cellulose artifacts.

Excitation Dynamics in Phycoerythrin 545: Modeling of Steady-State Spectra and Transient Absorption with Modified Redfield Theory

PubMed Central

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

2010-01-01

Abstract 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

Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy.

PubMed

Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

2013-11-04

We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated.

Absorption spectra of PTCDI: A combined UV-Vis and TD-DFT study

NASA Astrophysics Data System (ADS)

Oltean, Mircea; Calborean, Adrian; Mile, George; Vidrighin, Mihai; Iosin, Monica; Leopold, Loredana; Maniu, Dana; Leopold, Nicolae; Chiş, Vasile

2012-11-01

Absorption spectra of PTCDI (3,4,9,10-perylene-tetracarboxylic-diimide) have been investigated in chloroform, N,N'-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). While no signature of assembled PTCDI molecules is observed in chloroform solution, distinct bands assigned to their aggregation have been identified in DMF and DMSO solutions. PTCDI monomers show very similar absorption patterns in chloroform and DMSO solutions. Experimental data, including the vibronic structure of the absorption spectra were explained based on the Franck-Condon approximation and quantum chemical results obtained at PBE0-DCP/6-31+G(d,p) level of theory. Geometry optimization of the first excited state leads to a nice agreement between the calculated adiabatic transition energies and experimental data.

Two modes of longe-range orientation of DNA bases realized upon compaction.

PubMed Central

Yevdokimov YuM; Salyanov, V I; Berg, H

1981-01-01

Formation of compact particles from linear DNA-anthracycline complexes is accompanied by appearance of intense bands in the CD spectra in the region of absorption of DNA bases (UV-region) and in the region of absorption of anthracycline chromophores (visible region). The intense (positive or negative) bands in the region of anthracycline absorption demonstrate an ordered helical location of anthracycline molecules on the DNA template. This fact, in its turn, is related to formation of the DNA superstructure in PEG-containing water-salt solutions with a long-range orientation of nitrogen bases. Possible types of DNA superstructures and the relation between the local- and the long-range order of bases in the DNA superstructure are discussed. PMID:6938929

Spectroscopy for Industrial Applications: High-Temperature Processes

NASA Astrophysics Data System (ADS)

Fateev, Alexander; Grosch, Helge; Clausen, Sonnik; Barton, Emma J.; Yurchenko, Sergei N.; Tennyson, Jonathan

2014-06-01

The continuous development of the spectroscopic databases brings new perspectives in the environmental and industrial on-line process control, monitoring and stimulates further optical sensor developments. This is because no calibration gases are needed and, in general, temperature-dependent spectral absorption features gases of interest for a specific instrument can in principle be calculated by knowing only the gas temperature and pressure in the process under investigation/monitoring. The latest HITRAN-2012 database contains IR/UV spectral data for 47 molecules and it is still growing. However use of HITRAN is limited to low-temperature processes (< 400 K) and therefor can be used for absorption spectra calculations at limited temperature/pressure ranges. For higher temperatures, the HITEMP-2010 database is available. Only a few molecules CO2, H2O, CO and NO are those of interest for e.g. various combustion and astronomical applications are included. In the recent few years, several efforts towards a development of hot line lists have been made; those have been implemented in the latest HITRAN2012 database1. High-resolution absorption measurements of NH3 (IR, 0.1 cm-1) and phenol (UV, 0.019 nm) on a flow gas cell2 up to 800 K are presented. Molecules are of great interest in various high-temperature environments including exoplanets, combustion and gasification. Measured NH3 hot lines have been assigned and spectra have been compared with that obtained by calculations based on the BYTe hot line list1. High-temperature NH3 absorption spectra have been used in the analysis of in situ high-resolution IR absorption measurements on the producer gas in low-temperature gasification process on a large scale. High-resolution UV temperature-dependent absorption cross-sections of phenol are reported for the first time. All UV data have been calibrated by relevant GC/MS measurements. Use of the data is demonstrated by the analysis of in situ UV absorption measurements on a small-scale low-temperature gasifier. A comparison between in situ, gas extraction and conventional gas sampling measurements is presented. Overall the presentation shows an example of successful industrial and academic partnerships within the framework of national and international ongoing projects.

Application of support vector machine method for the analysis of absorption spectra of exhaled air of patients with broncho-pulmonary diseases

NASA Astrophysics Data System (ADS)

Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Tuzikov, Sergei A.; Yumov, Evgeny L.

2014-11-01

The results of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with respiratory diseases (chronic obstructive pulmonary disease, pneumonia and lung cancer) are presented. The absorption spectra of exhaled breath of all volunteers were measured, the classification methods of the scans of the absorption spectra were applied, the sensitivity/specificity of the classification results were determined. It were obtained a result of nosological in pairs classification for all investigated volunteers, indices of sensitivity and specificity.

Light Absorption and Excitation-Emission Fluorescence of Urban Organic Aerosol Components and Their Relationship to Chemical Structure.

PubMed

Chen, Qingcai; Ikemori, Fumikazu; Mochida, Michihiro

2016-10-18

The present study used a combination of solvent and solid-phase extractions to fractionate organic compounds with different polarities from total suspended particulates in Nagoya, Japan, and their optical characteristics were obtained on the basis of their UV-visible absorption spectra and excitation-emission matrices (EEMs). The relationship between their optical characteristics and chemical structures was investigated based on high-resolution aerosol mass spectra (HR-AMS spectra), soft ionization mass spectra and Fourier transform infrared (FT-IR) spectra. The major light-absorption organics were less polar organic fractions, which tended to have higher mass absorption efficiencies (MAEs) and lower wavelength dependent Ångström exponents (Å) than the more polar organic fractions. Correlation analyses indicate that organic compounds with O and N atoms may contribute largely to the total light absorption and fluorescence of the organic aerosol components. The extracts from the aerosol samples were further characterized by a classification of the EEM profiles using a PARAFAC model. Different fluorescence components in the aerosol organic EEMs were associated with specific AMS ions and with different functional groups from the FT-IR analysis. These results may be useful to determine and further classify the chromophores in atmospheric organic aerosols using EEM spectroscopy.

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…

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.

Method and apparatus for aerosol particle absorption spectroscopy

DOEpatents

Campillo, Anthony J.; Lin, Horn-Bond

1983-11-15

A method and apparatus for determining the absorption spectra, and other properties, of aerosol particles. A heating beam source provides a beam of electromagnetic energy which is scanned through the region of the spectrum which is of interest. Particles exposed to the heating beam which have absorption bands within the band width of the heating beam absorb energy from the beam. The particles are also illuminated by light of a wave length such that the light is scattered by the particles. The absorption spectra of the particles can thus be determined from an analysis of the scattered light since the absorption of energy by the particles will affect the way the light is scattered. Preferably the heating beam is modulated to simplify the analysis of the scattered light. In one embodiment the heating beam is intensity modulated so that the scattered light will also be intensity modulated when the particles absorb energy. In another embodiment the heating beam passes through an interferometer and the scattered light reflects the Fourier Transform of the absorption spectra.

Total absorption spectroscopy of fission fragments relevant for reactor antineutrino spectra

DOE PAGES

Fallot, M.; Porta, A.; Meur, L. Le; ...

2017-09-13

Here, the accurate determination of reactor antineutrino spectra remains a very active research topic for which new methods of study have emerged in recent years. Indeed, following the long-recognized reactor anomaly (measured antineutrino deficit in short baseline reactor experiments when compared with spectral predictions), the three international reactor neutrino experiments Double Chooz, Daya Bay and Reno have recently demonstrated the existence of spectral distortions in their measurements with respect to the same predictions. These spectral predictions were obtained through the conversion of integral beta-energy spectra obtained at the ILL research reactor. Several studies have shown that the underlying nuclear physicsmore » required for the conversion of these spectra into antineutrino spectra is not totally understood. An alternative to such converted spectra is a complementary approach that consists of determining the antineutrino spectrum by means of the measurement and processing of nuclear data. The beta properties of some key fission products suffer from the pandemonium effect which can be circumvented by the use of the Total Absorption Gamma-ray Spectroscopy technique (TAGS). The two main contributors to the Pressurized Water Reactor antineutrino spectrum in the region where the spectral distortion has been observed are 92Rb and 142Cs, which have been measured at the radioactive beam facility of the University of Jyvaskyla in two TAGS experiments. We present the results of the analysis of the TAGS measurements of the β-decay properties of 92Rb along with preliminary results on 142Cs and report on the measurements already performed.« less

Total absorption spectroscopy of fission fragments relevant for reactor antineutrino spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fallot, M.; Porta, A.; Meur, L. Le

Here, the accurate determination of reactor antineutrino spectra remains a very active research topic for which new methods of study have emerged in recent years. Indeed, following the long-recognized reactor anomaly (measured antineutrino deficit in short baseline reactor experiments when compared with spectral predictions), the three international reactor neutrino experiments Double Chooz, Daya Bay and Reno have recently demonstrated the existence of spectral distortions in their measurements with respect to the same predictions. These spectral predictions were obtained through the conversion of integral beta-energy spectra obtained at the ILL research reactor. Several studies have shown that the underlying nuclear physicsmore » required for the conversion of these spectra into antineutrino spectra is not totally understood. An alternative to such converted spectra is a complementary approach that consists of determining the antineutrino spectrum by means of the measurement and processing of nuclear data. The beta properties of some key fission products suffer from the pandemonium effect which can be circumvented by the use of the Total Absorption Gamma-ray Spectroscopy technique (TAGS). The two main contributors to the Pressurized Water Reactor antineutrino spectrum in the region where the spectral distortion has been observed are 92Rb and 142Cs, which have been measured at the radioactive beam facility of the University of Jyvaskyla in two TAGS experiments. We present the results of the analysis of the TAGS measurements of the β-decay properties of 92Rb along with preliminary results on 142Cs and report on the measurements already performed.« less

Amplification of anharmonicities in multiphoton vibrational action spectra.

PubMed

Calvo, F; Parneix, P

2012-01-16

The influence of one or several infrared laser pulses on the stability of bare and argon-tagged sodium chloride clusters is investigated theoretically by a combination of computational methods involving explicit molecular dynamics and properly calibrated unimolecular rate theories. The fragmentation spectra obtained by varying the laser frequency in the far-IR range is compared to the linear absorption spectrum resulting from the dipole moment autocorrelation function. Under appropriate laser field parameters, the action spectra are found to resemble the absorption spectra quite accurately in terms of positions, line widths, and even relative intensities. However, the action spectra exhibit residual and systematic redshifts of a few percent, which are partly due to the finite spectral bandwidth but are amplified by the progressive heating by the laser. A quantitative analysis suggests that these anharmonicity effects should generally arise upon multiple photon absorption. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Function of terahertz spectra in monitoring the decomposing process of biological macromolecules and in investigating the causes of photoinhibition.

PubMed

Qu, Yuangang; Zhang, Shuai; Lian, Yuji; Kuang, Tingyun

2017-03-01

Chlorophyll a and β-carotene play an important role in harvesting light energy, which is used to drive photosynthesis in plants. In this study, terahertz (THz) and visible range spectra of chlorophyll a and β-carotene and their changes under light treatment were investigated. The results show that the all THz transmission and absorption spectra of chlorophyll a and β-carotene changed upon light treatment, with the maximum changes at 15 min of illumination indicating the greatest changes of the collective vibrational mode of chlorophyll a and β-carotene. The absorption spectra of chlorophyll a in the visible light region decreased upon light treatment, signifying the degradation of chlorophyll a molecules. It can be inferred from these results that the THz spectra are very sensitive in monitoring the changes of the collective vibrational mode, despite the absence of changes in molecular configuration. The THz spectra can therefore be used to monitor the decomposing process of biological macromolecules; however, visible absorption spectra can only be used to monitor the breakdown extent of biological macromolecules.

A new method for detecting velocity shifts and distortions between optical spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, Tyler M.; Murphy, Michael T., E-mail: tevans@astro.swin.edu.au

2013-12-01

Recent quasar spectroscopy from the Very Large Telescope (VLT) and Keck suggests that fundamental constants may not actually be constant. To better confirm or refute this result, systematic errors between telescopes must be minimized. We present a new method to directly compare spectra of the same object and measure any velocity shifts between them. This method allows for the discovery of wavelength-dependent velocity shifts between spectra, i.e., velocity distortions, that could produce spurious detections of cosmological variations in fundamental constants. This 'direct comparison' method has several advantages over alternative techniques: it is model-independent (cf. line-fitting approaches), blind, in that spectralmore » features do not need to be identified beforehand, and it produces meaningful uncertainty estimates for the velocity shift measurements. In particular, we demonstrate that, when comparing echelle-resolution spectra with unresolved absorption features, the uncertainty estimates are reliable for signal-to-noise ratios ≳7 per pixel. We apply this method to spectra of quasar J2123–0050 observed with Keck and the VLT and find no significant distortions over long wavelength ranges (∼1050 Å) greater than ≈180 m s{sup –1}. We also find no evidence for systematic velocity distortions within echelle orders greater than 500 m s{sup –1}. Moreover, previous constraints on cosmological variations in the proton-electron mass ratio should not have been affected by velocity distortions in these spectra by more than 4.0 ± 4.2 parts per million. This technique may also find application in measuring stellar radial velocities in search of extra-solar planets and attempts to directly observe the expansion history of the universe using quasar absorption spectra.« less

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3-micrometers Region: Role of Periphery

NASA Technical Reports Server (NTRS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2017-01-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3-micrometers absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 per cm range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3-micrometers region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3-micrometers band, and on features such as the two-component emission character of this band and the 3-micrometers emission plateau.

High-resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3 μm Region: Role of Periphery

NASA Astrophysics Data System (ADS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

Improving Optical Absorption Models for Harsh Planetary Atmospheres: Laboratory Spectroscopy at Venus Surface Conditions

NASA Astrophysics Data System (ADS)

Cole, Ryan Kenneth; Schroeder, Paul James; Diego Draper, Anthony; Rieker, Gregory Brian

2018-06-01

Modelling absorption spectra in high pressure, high temperature environments is complicated by the increased relevance of higher order collisional phenomena (e.g. line mixing, collision-induced absorption, finite duration of collisions) that alter the spectral lineshape. Accurate reference spectroscopy in these conditions is of interest for mineralogy and radiative transfer studies of Venus as well as other dense planetary atmospheres. We present a new, high pressure, high temperature absorption spectroscopy facility at the University of Colorado Boulder. This facility employs a dual frequency comb absorption spectrometer to record broadband (500nm), high resolution (~0.002nm) spectra in conditions comparable to the Venus surface (730K, 90bar). Measurements of the near-infrared spectrum of carbon dioxide at high pressure and temperature will be compared to modeled spectra extrapolated from the HITRAN 2016 database as well as other published models that include additional collisional physics. This comparison gives insight into the effectiveness of existing absorption databases for modeling the lower Venus atmosphere as well as the need to expand absorption models to suit these conditions.

Ultra-violet and visible absorption characterization of explosives by differential reflectometry.

PubMed

Dubroca, Thierry; Moyant, Kyle; Hummel, Rolf E

2013-03-15

This study presents some optical properties of TNT (2,4,6-trinitrotoluene), RDX, HMX and tetryl, specifically their absorption spectra as a function of concentration in various solvents in the ultraviolet and visible portion of the electromagnetic spectrum. We utilize a standoff explosives detection method, called differential reflectometry (DR). TNT was diluted in six different solvents (acetone, acetonitrile, ethanol, ethyl acetate, methanol, and toluene), which allowed for a direct comparison of absorption features over a wide range of concentrations. A line-shape analysis was adopted with great accuracy (R(2)>0.99) to model the absorption features of TNT in differential reflectivity spectra. We observed a blue shift in the pertinent absorption band with decreasing TNT concentration for all solvents. Moreover, using this technique, it was found that for all utilized solvents the concentration of TNT as well as of RDX, HMX, and tetryl, measured as a function of the transition wavelength of the ultra-violet absorption edge in differential reflectivity spectra shows three distinct regions. A model is presented to explain this behavior which is based on intermolecular hydrogen bonding of explosives molecules with themselves (or lack thereof) at different concentrations. Other intermolecular forces such as dipole-dipole interactions, London dispersion forces and π-stacking contribute to slight variations in the resulting spectra, which were determined to be rather insignificant in comparison to hydrogen bonding. The results are aimed towards a better understanding of the DR spectra of explosives energetic materials. Copyright © 2012 Elsevier B.V. All rights reserved.

Molecular hydrogen absorption systems in Sloan Digital Sky Survey

NASA Astrophysics Data System (ADS)

Balashev, S. A.; Klimenko, V. V.; Ivanchik, A. V.; Varshalovich, D. A.; Petitjean, P.; Noterdaeme, P.

2014-05-01

We present a systematic search for molecular hydrogen absorption systems at high redshift in quasar spectra from the Sloan Digital Sky Survey (SDSS)-II Data Release 7 and SDSS-III Data Release 9. We have selected candidates using a modified profile fitting technique taking into account that the Lyα forest can effectively mimic H2 absorption systems at the resolution of SDSS data. To estimate the confidence level of the detections, we use two methods: a Monte Carlo sampling and an analysis of control samples. The analysis of control samples allows us to define regions of the spectral quality parameter space where H2 absorption systems can be confidently identified. We find that H2 absorption systems with column densities log NH2 > 19 can be detected in only less than 3 per cent of SDSS quasar spectra. We estimate the upper limit on the detection rate of saturated H2 absorption systems (NH2 > 19) in damped Lyα (DLA) systems to be about 7 per cent. We provide a sample of 23 confident H2 absorption system candidates that would be interesting to follow up with high-resolution spectrographs. There is a 1σ r - i colour excess and non-significant AV extinction excess in quasar spectra with an H2 candidate compared to standard DLA-bearing quasar spectra. The equivalent widths of C II, Si II and Al III (but not Fe II) absorptions associated with H2 candidate DLAs are larger compared to standard DLAs. This is probably related to a larger spread in velocity of the absorption lines in the H2-bearing sample.

A systematic approach to determining the properties of an iodine absorption cell for high-precision radial velocity measurements

NASA Astrophysics Data System (ADS)

Perdelwitz, V.; Huke, P.

2018-06-01

Absorption cells filled with diatomic iodine are frequently employed as wavelength reference for high-precision stellar radial velocity determination due their long-term stability and low cost. Despite their wide-spread usage in the community, there is little documentation on how to determine the ideal operating temperature of an individual cell. We have developed a new approach to measuring the effective molecular temperature inside a gas absorption cell and searching for effects detrimental to a high precision wavelength reference, utilizing the Boltzmann distribution of relative line depths within absorption bands of single vibrational transitions. With a high resolution Fourier transform spectrometer, we took a series of 632 spectra at temperatures between 23 °C and 66 °C. These spectra provide a sufficient basis to test the algorithm and demonstrate the stability and repeatability of the temperature determination via molecular lines on a single iodine absorption cell. The achievable radial velocity precision σRV is found to be independent of the cell temperature and a detailed analysis shows a wavelength dependency, which originates in the resolving power of the spectrometer in use and the signal-to-noise ratio. Two effects were found to cause apparent absolute shifts in radial velocity, a temperature-induced shift of the order of ˜1 ms-1K-1 and a more significant effect resulting in abrupt jumps of ≥50 ms-1 is determined to be caused by the temperature crossing the dew point of the molecular iodine.

Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

DOE PAGES

Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

2015-03-02

We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~10 6 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10 7 laser pulses, wemore » also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

Alkaline transition of pseudoazurin Met16X mutant proteins: protein stability influenced by the substitution of Met16 in the second sphere coordination.

PubMed

Abdelhamid, Rehab F; Obara, Yuji; Kohzuma, Takamitsu

2008-01-01

Several blue copper proteins are known to change the active site structure at alkaline pH (alkaline transition). Spectroscopic studies of Met16Phe, Met16Tyr, Met16Trp, and Met16Val pseudoazurin variants were performed to investigate the second sphere role through alkaline transition. The visible electronic absorption and resonance Raman spectra of Met16Phe, Met16Tyr, and Met16Trp variants showed the increasing of axial component at pH approximately 11 like wild-type PAz. The visible electronic absorption and far-UV CD spectra of Met16Val demonstrated that the destabilization of the protein structure was triggered at pH>11. Resonance Raman (RR) spectra of PAz showed that the intensity-weighted averaged Cu-S(Cys) stretching frequency was shifted to higher frequency region at pH approximately 11. The higher frequency shift of Cu-S(Cys) bond is implied the stronger Cu-S(Cys) bond at alkaline transition pH approximately 11. The visible electronic absorption and far-UV CD spectra of Met16X PAz revealed that the Met16Val variant is denatured at pH>11, but Met16Phe, Met16Tyr, and Met16Trp mutant proteins are not denatured even at pH>11. These observations suggest that Met16 is important to maintain the protein structure through the possible weak interaction between methionine -SCH3 part and coordinated histidine imidazole moiety. The introduction of pi-pi interaction in the second coordination sphere may be contributed to the enhancement of protein structure stability.

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…

Understanding THz spectra of aqueous solutions: glycine in light and heavy water.

PubMed

Sun, Jian; Niehues, Gudrun; Forbert, Harald; Decka, Dominique; Schwaab, Gerhard; Marx, Dominik; Havenith, Martina

2014-04-02

THz spectroscopy of aqueous solutions has been established as of recently to be a valuable and complementary experimental tool to provide direct insights into the solute-solvent coupling due to hydrogen-bond dynamics involving interfacial water. Despite much experimental progress, understanding THz spectra in terms of molecular motions, akin to mid-infrared spectra, still remains elusive. Here, using the osmoprotectant glycine as a showcase, we demonstrate how this can be achieved by combining THz absorption spectroscopy and ab initio molecular dynamics. The experimental THz spectrum is characterized by broad yet clearly discernible peaks. Based on substantial extensions of available mode-specific decomposition schemes, the experimental spectrum can be reproduced by theory and assigned on an essentially quantitative level. This joint effort reveals an unexpectedly clear picture of the individual contributions of molecular motion to the THz absorption spectrum in terms of distinct modes stemming from intramolecular vibrations, rigid-body-like hindered rotational and translational motion, and specific couplings to interfacial water molecules. The assignment is confirmed by the peak shifts observed in the THz spectrum of deuterated glycine in heavy water, which allow us to separate the distinct modes experimentally.

Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions.

PubMed

Yamada, Michio; Slanina, Zdenek; Mizorogi, Naomi; Muranaka, Atsuya; Maeda, Yutaka; Nagase, Shigeru; Akasaka, Takeshi; Kobayashi, Nagao

2013-03-14

We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C(2v)-C(82), La(2)@I(h)-C(80), and Sc(3)N@I(h)-C(80) can be assigned using these techniques. Particularly, a difference in the electronic transitions between La(2)@I(h)-C(80) and Sc(3)N@I(h)-C(80), which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La(2)@I(h)-C(80) were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La(2)@I(h)-C(80), although no marked difference exists in their absorption spectra.

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

Spectral line shapes of collision-induced light scattering (CILS) and collision-induced absorption (CIA) using isotropic intermolecular potential for H2-Ar

NASA Astrophysics Data System (ADS)

El-Kader, M. S. A.; Godet, J.-L.; El-Sadek, A. A.; Maroulis, G.

2017-10-01

Quantum mechanical line shapes of collision-induced light scattering at room temperature (295 K) and collision-induced absorption at T = 195 K are computed for gaseous mixtures of molecular hydrogen and argon using theoretical values for pair-polarisability trace and anisotropy and induced dipole moments as input. Comparison with other theoretical spectra of isotropic and anisotropic light scattering and measured spectra of absorption shows satisfactory agreement, for which the uncertainty in measurement of its spectral moments is seen to be large. Ab initio models of the trace and anisotropy polarisability which reproduce the recent spectra of scattering are given. Empirical model of the dipole moment which reproduce the experimental spectra and the first three spectral moments more closely than the fundamental theory are also given. Good agreement between computed and/or experimental line shapes of both absorption and scattering is obtained when the potential model which is constructed from the transport and thermo-physical properties is used.

Gigahertz-peaked Spectra Pulsars and Thermal Absorption Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kijak, J.; Basu, R.; Lewandowski, W.

2017-05-10

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

[The change in optical spectra from solid and liquid solution of copper phthalocyanines derivatives].

PubMed

Zheng, Xiao-pan; He, Zhi-qun; Zhang, Chun-xiu; Xu, Zheng; Wang, Yong-sheng

2006-06-01

In the present work, the change in electronic absorption spectra from three copper phthalocyanines (CuPc, tb-CuPc, oo-CuPc) in different environments was investigated. The mechanism of red shift Q-band absorption from the three species in an organic solvent before and after protonation was discussed. This was used to compare with those dispersed in solid films. The relation between the molecular interactions and the spectra change was studied. In a combination of POM, DSC and XRD techniques, the structure and morphology of the thin films were characterised. It was found that the molecules in the doped matrices of PC were associated or aggregated. This association and hence the corresponding change in absorption spectra cannot be altered by the modification of dopant concentration.

First Principles Optical Absorption Spectra of Organic Molecules Adsorbed on Titania Nanoparticles

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol; Ogut, Serdar; Mete, Ersen; Gulseren, Oguz; Ellialtioglu, Sinasi

2012-02-01

We present results from first principles computations on passivated rutile TiO2 nanoparticles in both free-standing and dye-sensitized configurations to investigate the size dependence of their optical absorption spectra. The computations are performed using time-dependent density functional theory (TDDFT) as well as GW-Bethe-Salpeter-Equation (GWBSE) methods and compared with each other. We interpret the first principles spectra for free-standing TiO2 nanoparticles within the framework of the classical Mie-Gans theory using the bulk dielectric function of TiO2. We investigate the effects of the titania support on the absorption spectra of a particular set of perylene-diimide (PDI) derived dye molecules, namely brominated PDI (Br2C24H8N2O4) and its glycine and aspartine derivatives.

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

Vibronic spectra of Cu(2+) in ZnTe

NASA Technical Reports Server (NTRS)

Volz, M. P.; Su, C.-H.; Lehoczky, S. L.; Szofran, F. R.

1992-01-01

Infrared-absorption spectra of substitutional Cu(2+) ions in ZnTe have been measured at 4.6 K. Several distinct absorption peaks are observed between 800 and 2000/cm. Absorption peaks at 1002 and 1069/cm are identified as zero-phonon lines arising from 2T2-2E transitions. Between 1069 and 2000/cm, several sets of sharp absorption lines are seen to recur regularly at an interval of 210/cm, corresponding to the LO phonon energy. Within each set distinct vibronic sidebands that cannot be identified with critical-point energies of TA, LA, TO or LO phonon modes are observed. A dynamic Jahn-Teller effect, involving coupling between a single-phonon mode and the electronic states of the 2E level, is proposed to account for the observed spectra.

Substituent and solvent effects on the UV/Vis absorption spectra of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones

NASA Astrophysics Data System (ADS)

Ušćumlić, Gordana S.; Mijin, Dusanˇ Z. ˇ; Valentić, Nataša V.; Vajs, Vlatka V.; Sušić, Biljana M.

2004-10-01

Absorption spectra of ten 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones have been recorded in fifteen solvents in the range 200-600 nm. The substituents at the phenyl nucleus are as follows: OH, OCH 3, CH 3, C 2H 5, H, Cl, Br, I, COOH and NO 2. The effects of substituents on the absorption spectra of investigated compounds are interpreted by correlation of absorption frequencies with simple Hammett equation. The effects of solvent polarity and solvent/solute hydrogen bonding interactions are analyzed by means of linear solvation energy relationships concept proposed by Kamlet and Taft. The azo-hydrazone tuatomeric equilibration is found to depend upon substituents as well as on solvents.

Selective laser spectroscopy of molecules and ions in solids: a history, fundamentals and applications

NASA Astrophysics Data System (ADS)

Sapozhnikov, Michael

2018-03-01

A history of the development of selective laser spectroscopy is presented, beginning with a pioneering work by Yu. V. Denisov and V. A. Kizel in 1967, who were the first to demonstrate the possibility of removing the inhomogeneous broadening of luminescence spectra of impurity ions in glasses upon monochromatic resonance excitation. Selective excitation of optical centers can be achieved due to existence of zero-phonon transitions corresponding to narrow homogeneous zero-phonon lines in the spectra of impurity centers in solids, which are hidden in broad inhomogeneous optical bands upon usual nonselective excitation. The fundamentals of zero-phonon transition spectroscopy are considered and the mechanism of removing the inhomogeneous broadening of optical spectra of ions and molecules in crystals and amorphous solids under selective laser excitation of luminescence and persistent hole burning in absorption spectra is presented in detail. Various applications of selective laser spectroscopy for fundamental and applied studies are discussed.

Non-resonant inelastic x-ray scattering spectra of lithiated titanium oxides for battery applications

NASA Astrophysics Data System (ADS)

Nagle, Kenneth; Balasubramanian, Mali; Johnson, Christopher; Seidler, Gerald; Belharouak, Ilias

2008-03-01

Although lithium-ion batteries now see widespread use, there remain considerable questions concerning the basic solid state chemistry of both electrodes. Improved understanding of the local electronic structure, particularly the mechanism of charge transfer upon insertion and removal of lithium, could lead to innovation in battery design and improved performance. We present non-resonant inelastic x-ray scattering (NRIXS) spectra from 2p initial states in titanium; these spectra are among the first recorded for such states in a transition metal. These spectra were obtained using the lower energy resolution inelastic x-ray scattering (LERIX) spectrometer, which is capable of making simultaneous measurements at nineteen values of momentum transfer. We demonstrate the ability to obtain soft x-ray absorption-like information using a bulk-sensitive, hard x-ray technique. In addition, at high momentum transfer NRIXS provides information about non-dipole transitions that are inaccessible by soft x-ray spectroscopic methods.

Imaging at an x-ray absorption edge using free electron laser pulses for interface dynamics in high energy density systems [Resonant phase contrast imaging for interface physics

DOE PAGES

Beckwith, M. A.; Jiang, S.; Schropp, A.; ...

2017-05-01

Tuning the energy of an x-ray probe to an absorption line or edge can provide material-specific measurements that are particularly useful for interfaces. Simulated hard x-ray images above the Fe K-edge are presented to examine ion diffusion across an interface between Fe 2O 3 and SiO 2 aerogel foam materials. The simulations demonstrate the feasibility of such a technique for measurements of density scale lengths near the interface with submicron spatial resolution. A proof-of-principle experiment is designed and performed at the Linac coherent light source facility. Preliminary data show the change of the interface after shock compression and heating withmore » simultaneous fluorescence spectra for temperature determination. Here, the results provide the first demonstration of using x-ray imaging at an absorption edge as a diagnostic to detect ultrafast phenomena for interface physics in high-energy-density systems.« less

Combined "dual" absorption and fluorescence smartphone spectrometers.

PubMed

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

2015-04-15

A combined "dual" absorption and fluorescence smartphone spectrometer is demonstrated. The optical sources used in the system are the white flash LED of the smartphone and an orthogonally positioned and interchangeable UV (λ_ex=370  nm) and blue (λ_ex=450  nm) LED. The dispersive element is a low-cost, nano-imprinted diffraction grating coated with Au. Detection over a 300 nm span with 0.42 nm/pixel resolution was carried out with the camera CMOS chip. By integrating the blue and UV excitation sources into the white LED circuitry, the entire system is self-contained within a 3D printed case and powered from the smartphone battery; the design can be scaled to add further excitation sources. Using a customized app, acquisition of absorption and fluorescence spectra are demonstrated using a blue-absorbing and green-emitting pH-sensitive amino-naphthalimide-based fluorescent probe and a UV-absorbing and blue-emitting Zn²⁺-sensitive fluoro-ionophore.

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions.

PubMed

Abramczyk, H; Brozek-Płuska, B; Kurczewski, K; Kurczewska, M; Szymczyk, I; Krzyczmonik, P; Błaszczyk, T; Scholl, H; Czajkowski, W

2006-07-20

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.

Electrically tunable coherent optical absorption in graphene with ion gel.

PubMed

Thareja, Vrinda; Kang, Ju-Hyung; Yuan, Hongtao; Milaninia, Kaveh M; Hwang, Harold Y; Cui, Yi; Kik, Pieter G; Brongersma, Mark L

2015-03-11

We demonstrate electrical control over coherent optical absorption in a graphene-based Salisbury screen consisting of a single layer of graphene placed in close proximity to a gold back reflector. The screen was designed to enhance light absorption at a target wavelength of 3.2 μm by using a 600 nm-thick, nonabsorbing silica spacer layer. An ionic gel layer placed on top of the screen was used to electrically gate the charge density in the graphene layer. Spectroscopic reflectance measurements were performed in situ as a function of gate bias. The changes in the reflectance spectra were analyzed using a Fresnel based transfer matrix model in which graphene was treated as an infinitesimally thin sheet with a conductivity given by the Kubo formula. The analysis reveals that a careful choice of the ionic gel layer thickness can lead to optical absorption enhancements of up to 5.5 times for the Salisbury screen compared to a suspended sheet of graphene. In addition to these absorption enhancements, we demonstrate very large electrically induced changes in the optical absorption of graphene of ∼3.3% per volt, the highest attained so far in a device that features an atomically thick active layer. This is attributable in part to the more effective gating achieved with the ion gel over the conventional dielectric back gates and partially by achieving a desirable coherent absorption effect linked to the presence of the thin ion gel that boosts the absorption by 40%.

Facile synthesis of a two-photon fluorescent probe based on pyrimidine 2-isothiocyanate and its application in bioimaging.

PubMed

Yang, Jie; Hu, Wei; Li, Huirong; Hou, Hanna; Tu, Yi; Liu, Bo

2018-04-18

Two-photon microscopy imaging has been widely applied in biological imaging, but the development of two-photon absorption probes is obviously lagging behind in the development of imaging technology. In this paper, a two-photon fluorescent probe (1) based on pyrimidine 2-isothiocyanate has been designed and synthesized through a simple method for two-photon biological imaging. Probe 1 was able to couple effectively with the amino groups on biomolecules. To verify the reactivity of the isothiocyanate group on probe 1 and the amine groups on the biomolecules, d-glucosamine was chosen as a model biomolecule to conjugate with probe 1. The result showed that probe 1 could effectively conjugate with d-glucosamine to synthesize probe 2, and the yield of probe 2 was 83%. After conjugating with d-glucosamine, linear absorption spectra, single-photon fluorescence spectra, and two-photon fluorescence spectra of probes 1 and 2 did not present significant changes. Probes 1 and 2 exhibited high fluorescence quantum yields (0.71-0.79) in toluene and chloroform. They also exhibited different photo-physical properties in solvents with different polarities. The two-photon absorption cross-section of probe 1 was 953 GM in toluene. In addition, probe 1 could be effectively conjugated with transferrin, and the conjugated probe (Tf-1) could be transported into Hep G2 cells through a receptor-mediated process for biological imaging. These results demonstrate that such probes are expected to have great potential applications in two-photon fluorescence bioimaging.

The Magellan Evolution of Galaxies Spectroscopic and Ultraviolet Reference Atlas (MegaSaura). II. Stacked Spectra

NASA Astrophysics Data System (ADS)

Rigby, J. R.; Bayliss, M. B.; Chisholm, J.; Bordoloi, R.; Sharon, K.; Gladders, M. D.; Johnson, T.; Paterno-Mahler, R.; Wuyts, E.; Dahle, H.; Acharyya, A.

2018-01-01

We stack the rest-frame ultraviolet spectra of N = 14 highly magnified gravitationally lensed galaxies at redshifts 1.6< z< 3.6. The resulting new composite spans 900< {λ }{rest}< 3000 Å, with a peak signal-to-noise ratio (S/N) of 103 per spectral resolution element (∼100 km s‑1). It is the highest S/N, highest spectral resolution composite spectrum of z ∼ 2–3 galaxies yet published. The composite reveals numerous weak nebular emission lines and stellar photospheric absorption lines that can serve as new physical diagnostics, particularly at high redshift with the James Webb Space Telescope (JWST). We report equivalent widths to aid in proposing for and interpreting JWST spectra. We examine the velocity profiles of strong absorption features in the composite, and in a matched composite of z∼ 0 COS/HST galaxy spectra. We find remarkable similarity in the velocity profiles at z∼ 0 and z∼ 2, suggesting that similar physical processes control the outflows across cosmic time. While the maximum outflow velocity depends strongly on ionization potential, the absorption-weighted mean velocity does not. As such, the bulk of the high-ionization absorption traces the low-ionization gas, with an additional blueshifted absorption tail extending to at least ‑2000 km s‑1. We interpret this tail as arising from the stellar wind and photospheres of massive stars. Starburst99 models are able to replicate this high-velocity absorption tail. However, these theoretical models poorly reproduce several of the photospheric absorption features, indicating that improvements are needed to match observational constraints on the massive stellar content of star-forming galaxies at z∼ 2. We publicly release our composite spectra.

First Spectroscopic Identification of Massive Young Stellar Objects in the Galactic Center

NASA Technical Reports Server (NTRS)

An, Deokkeun; Ramirez, V.; Sellgren, Kris; Arendt, Richard G.; Boogert, A. C.; Schultheis, Mathias; Stolovy, Susan R.; Cotera, Angela S.; Robitaille, Thomas P.; Smith, Howard A.

2009-01-01

We report the detection of several molecular gas-phase and ice absorption features in three photometrically-selected young stellar object (YSO) candidates in the central 280 pc of the Milky Way. Our spectra, obtained with the Infrared Spectrograph (IRS) onboard the Spitzer Space Telescope, reveal gas-phase absorption from CO2 (15.0 microns), C2H2 (13.7 microns) and HCN (14.0 microns). We attribute this absorption to warm, dense gas in massive YSOs. We also detect strong and broad 15 microns CO2 ice absorption features, with a remarkable double-peaked structure. The prominent long-wavelength peak is due to CH3OH-rich ice grains, and is similar to those found in other known massive YSOs. Our IRS observa.tions demonstra.te the youth of these objects, and provide the first spectroscopic identification of massive YSOs in the Galactic Center.

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Near UV-Visible electronic absorption originating from charged amino acids in a monomeric protein† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00880e

PubMed Central

Prasad, Saumya; Mandal, Imon; Singh, Shubham; Paul, Ashim; Mandal, Bhubaneswar

2017-01-01

Electronic absorption spectra of proteins are primarily characterized over the ultraviolet region (185–320 nm) of the electromagnetic spectrum. While recent studies on peptide aggregates have revealed absorption beyond 350 nm, monomeric proteins lacking aromatic amino acids, disulphide bonds, and active site prosthetic groups are expected to remain optically silent beyond 250 nm. Here, in a joint theoretical and experimental investigation, we report the distinctive UV-Vis absorption spectrum between 250 nm [ε = 7338 M–1 cm–1] and 800 nm [ε = 501 M–1 cm–1] in a synthetic 67 residue protein (α3C), in monomeric form, devoid of aromatic amino acids. Systematic control studies with high concentration non-aromatic amino acid solutions revealed significant absorption beyond 250 nm for charged amino acids which constitute over 50% of the sequence composition in α3C. Classical atomistic molecular dynamics (MD) simulations of α3C reveal dynamic interactions between multiple charged sidechains of Lys and Glu residues present in α3C. Time-dependent density functional theory calculations on charged amino acid residues sampled from the MD trajectories of α3C reveal that the distinctive absorption features of α3C may arise from two different types of charge transfer (CT) transitions involving spatially proximal Lys/Glu amino acids. Specifically, we show that the charged amino (NH3+)/carboxylate (COO–) groups of Lys/Glu sidechains act as electronic charge acceptors/donors for photoinduced electron transfer either from/to the polypeptide backbone or to each other. Further, the sensitivity of the CT spectra to close/far/intermediate range of encounters between sidechains of Lys/Glu owing to the three dimensional protein fold can create the long tail in the α3C absorption profile between 300 and 800 nm. Finally, we experimentally demonstrate the sensitivity of α3C absorption spectrum to temperature and pH-induced changes in protein structure. Taken together, our investigation significantly expands the pool of spectroscopically active biomolecular chromophores and adds an optical 250–800 nm spectral window, which we term ProCharTS (Protein Charge Transfer Spectra), for label free probes of biomolecular structure and dynamics. PMID:28970921

Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

NASA Astrophysics Data System (ADS)

Schäfer, Julia M.; Inhester, Ludger; Son, Sang-Kil; Fink, Reinhold F.; Santra, Robin

2018-05-01

With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

Photoabsorption study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

NASA Technical Reports Server (NTRS)

Frigo, Sean P.; McNulty,Ian; Richmond, Robert C.; Ehret, Charles F.

2003-01-01

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include red phosphorus, hydrated sodium phosphate (Na3PO4 12 H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position, where each is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B.meguterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition, the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Photoabsorption Study of Bacillus megaterium, DNA and Related Biological Materials in the Phosphorus K-edge Region

NASA Technical Reports Server (NTRS)

Frigo, Sean P.; McNulty, Ian; Richmond, Robert C.; Ehret, Charles F.

2002-01-01

We have measured the x-ray transmission spectra of several biologically related samples in the phosphorus K-edge absorption region. These include elemental red phosphorus, hydrated sodium phosphate (Na3PO4.12H2O), deoxyribonucleic acid (DNA), adenosinetriphosphate (ATP), diolylphosphatidyl choline (DOPC), and Bacillus megaterium spores. Elemental red phosphorus essentially displays an edge-jump. All other spectra are similar in form and energy position. Each spectrum for these substances is dominated by a narrower, more intense first peak and a broader but less intense second peak. The corresponding K-edge absorption thresholds are shifted towards higher energy relative to that for elemental red phosphorus, as expected for increasing degrees of phosphorus oxidation. The B. megaterium spectrum has aspects common to both the phosphate and DNA spectra and is therefore interpreted as a composite of spectra arising from DNA/RNA and phosphates within the spore. The B. megaterium spore spectrum provides needed information for resonant radiation damage studies in the phosphorus K-edge absorption region by identifying candidate photoexcitations. In addition,the absorption spectra will be useful in macromolecular crystallography studies employing anomalous dispersion effects at the phosphorus K-edge.

Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Jeffries, J. B.; Hanson, R. K.

2009-01-01

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012 ←00001 band of CO2 near 2.0 μm (5000 cm-1) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO2 in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO2 sensor design are discussed.

[Seasonal changes of optical absorption properties of river and lake in East Liaohe River basin, Northeast China].

PubMed

Song, Yan Yan; Su, Dong Hui; Shao, Tian Tian

2017-06-18

The absorption characteristics of optically active constituents (OACs) in water column are important optical properties and basic parameters of establishing the inverse analysis model. Comparative analyses about seasonal variability of the optical absorption characteristics (phytoplankton, non-algal particles and chromophoric dissolved organic matter absorption characteristics) and water quality status of East Liaohe River basin were conducted based on the water samples in Erlong-hu Reservoir collected in June, September and October of 2011 and samples in East Liaohe River in October of 2012. The results demonstrated that the eutrophication status of Erlonghu Reservoir was lower in June, eutrophic in September and moderately eutrophic in October. Some of the sampling points of the East Liaohe River belonged to the middle trophic level and the other part belonged to the eutrophic level. The absorption coefficient of each component of water increased with increasing nutrient level. Besides, the absorption spectra of total suspended particulate of Erlonghu Reservoir in June and October were similar to that of non-algal particles, and chromophoric dissolved organic matter (CDOM) contributed most to the total absorption of water. The absorption spectra of total suspended particulate matter in September were similar to that of phytoplankton and phytoplankton was the dominant contributor to the total absorption. For samples of Erlonghu Reservoir in June and September, a ph (440) and total phosphorus (TP) were correlated closely with each other. Significant correlation between a ph (440) and dissolved organic carbon (DOC) of Erlonghu Reservoir in June was observed, while a d (440) was only correlated with Chla. There were positive correlations between a ph (675) and Chla, Carlson index (TLI) in Erlonghu Reservoir (September) and East Liaohe River. Obvious differences of water optical properties were found between river and lake located in the East Liaohe River basin as follows: There were two types of phytoplankton spectra curves of East Liaohe River and the contribution rates of different components varied greatly from sites to sites; Phytoplankton dominated spectral absorption in waters with high nutrition level (Erlonghu Reservoir in September and the East Liaohe River) while CDOM and the particles were both the main components for Erlonghu Reservoir in June and October; CDOM was composed of large-size molecules in waters of Erlonghu Reservoir in June and in the East Liaohe River in October and mainly of small-size molecules in Erlonghu Reservoir in September and October.

NO2 trace measurements by optical-feedback cavity-enhanced absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ventrillard-Courtillot, I.; Foldes, T.; Romanini, D.

2009-04-01

In order to reach the sub-ppb NO2 detection level required for environmental applications in remote areas, we are developing a spectrometer that exploits a technique that we introduced several years ago, named Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) [1]. It allows very sensitive and selective measurements, together with the realization of compact and robust set-ups as was subsequently demonstrated during measurements campaigns in harsh environments [2,3]. OF-CEAS benefits from the optical feedback (OF) to efficiently inject a cw-laser in a high finesse cavity (typically F >10 000). Absorption spectra are acquired on a small spectral region (~1 cm-1) that enables selective and quantitative measurements at a fast acquisition rate (~10 Hz) with a detection limit of several 10-10 cm-1 as reported in this paper. Spectra are obtained with high spectral resolution (~150 MHz) and are self calibrated by cavity rind-down measurements regularly performed (typically every second). Therefore, OF-CEAS appears very attractive for NO2 trace detection. This work is performed in the blue spectral region where NO2 has intense electronic transitions. Our setup involves a commercial extended cavity diode laser (ECDL) working at room temperature around 411nm. A first setup was developed [4] to demonstrate that OF sensitivity of ECDL is fully consistent with this technique, initially introduced with distributed feedback diode lasers in the near infrared region. In this paper we will report on a new set-up developed for in-situ measurements with proper mechanical, acoustic and thermal insulation. Additionally, new data processing was implemented allowing real time concentration measurements. It is based on a reference spectra recorded under controlled conditions by OF-CEAS and used later to fit the observed spectra. We will present measurements performed with calibrated NO2 reference samples demonstrating a good linearity of the apparatus. The minimum detectable absorption loss is estimated by considering the standard deviation of the spectra. We achieved better than 2x10-10 cm-1 for a single spectrum recorded in less than 100ms at 100mbar. This limit constitutes an improved of more than one order of magnitude as compare to the previous measurements reported in [4]. It leads to a detection limit of 3x108 molecules/cm3, corresponding to about 150pptv at 100mbar. At atmospheric pressure the same measurement would yield a detection limit of 15pptv assuming we can maintain the same level of sensitivity. But currently, works are under development to transfer the low minimum detectable absorption limit, already obtained for one spectrum, to a set of real time measurements. These are now limited by amplitude fluctuations of a few ppb from one spectrum to another one. [1] J. Morville, S. Kassi, M. Chenevier, and D. Romanini, Appl. Phys. B, 80, 1027 (2005). [2] D. Romanini, M. Chenevrier, S. Kassi, M. Schmidt, C. Valant, M. Ramonet, J. Lopez, and H.-J. Jost, Appl. Phys. B, 83, 659 (2006). [2] E.R.T. Kerstel, R.Q. Iannone, M. Chenevrier, S. Kassi, H.-J. Jost and D. Romanini, Appl. Phys. B, 84, 343 (2006). [4] I. Courtillot, J. Morville, V. Motto-Ros, and D. Romanini, Appl. Phys. B, 85, 407 (2006).

Inversion of the 11Bu and 21Ag electronic states of all-trans-1,6-diphenyl-1,3,5-hexatriene in carbon disulfide.

PubMed

Catalán, Javier

2017-10-11

From the analysis of UV/Vis absorption spectra, emission and excitation emission spectra of solutions of all-trans-1,6-diphenyl-1,3,5-hexatriene (DPH) in carbon disulfide (CS 2 ) within a wide range of temperatures, we can conclude that these spectra do not support the inversion of excited electronic states in DPH by an increased polarizability of the solvent as proposed by Kohler and Itoh. The proposal by Kohler and Itoh is widely accepted as an elegant demonstration of the inversion of the 1 1 Bu and 2 1 Ag states in the polyene DPH by a mere increase in the solvent polarizability. The evidence provided in this paper confirms, as has recently been proposed, that a ghost state as the first electronic state, 2 1 Ag, is not necessary to explain the photophysics of DPH. The photophysics of DPH is plausibly explicable with the 1 1 Bu state, which is directly excitable by photonic absorption from the fundamental electronic state of the compound. In this paper, we provide evidence that the UV/Vis spectra of DPH in CS 2 at 77 K are most likely generated from a molecular structure of DPH constrained by solid CS 2 , which is clearly distinct from that present in liquid CS 2 .

Theoretical model for optical properties of porphyrin

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Nga, Do T.; Phan, The-Long; Thanh, Le T. M.; Anh, Chu T.; Bernad, Sophie; Viet, N. A.

2014-12-01

We propose a simple model to interpret the optical absorption spectra of porphyrin in different solvents. Our model successfully explains the decrease in the intensity of optical absorption at maxima of increased wavelengths. We also prove the dependence of the intensity and peak positions in the absorption spectra on the environment. The nature of the Soret band is supposed to derive from π plasmon. Our theoretical calculations are consistent with previous experimental studies.

Atmospheric solar absorption measurements in the 9 to 11 mu m region using a diode laser heterodyne spectrometer

NASA Technical Reports Server (NTRS)

Harward, C. N.; Hoell, J. M., Jr.

1980-01-01

A tunable diode laser heterodyne radiometer was developed for ground-based measurements of atmospheric solar absorption spectra in the 8 to 12 microns spectral range. The performance and operating characteristics of this Tunable Infrared Heterodyne Radiometer (TIHR) are discussed along with atmospheric solar absorption spectra of HNO3, O3, CO2, and H2O in the 9 to 11 microns spectral region.

Kinetic and spectroscopic characterization of tungsten-substituted DMSO reductase from Rhodobacter sphaeroides.

PubMed

Pacheco, Josué; Niks, Dimitri; Hille, Russ

2018-03-01

We have examined the kinetic and spectroscopic properties of a tungsten-substituted form of DMSO reductase from Rhodobacter sphaeroides, an enzyme that normally possesses molybdenum. Partial reduction with sodium dithionite yields a well-resolved W(V) EPR signal of the so-called "high-g split" type that exhibits markedly greater g-anisotropy than the corresponding Mo(V) signal of the native form of the enzyme, with the g values shifted to higher magnetic field by as much as Δg ave  = 0.056. Deuteration of the enzyme confirms that the coupled proton is solvent-exchangeable, allowing us to accurately simulate the tungsten hyperfine coupling. Global curve-fitting analysis of UV/vis absorption spectra observed in the course of the reaction of the tungsten-substituted enzyme with sodium dithionite affords a well-defined absorption spectrum for the W(V) species. Surprisingly, the absorption spectrum for this species exhibits significantly larger molar extinction coefficients than either the reduced or the oxidized spectrum. This spectrum, in conjunction with those for fully oxidized W(VI) and fully reduced W(IV) enzyme, has been used to deconvolute the absorption spectra seen in the course of turnover, in the which enzyme is reacted with sodium dithionite and DMSO, demonstrating that the W(V) is an authentic catalytic intermediate that accumulates to approximately 50% of the total enzyme in the steady state.

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE 3 μ m REGION: ROLE OF PERIPHERY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maltseva, Elena; Petrignani, Annemieke; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μ m absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm{sup −1} range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μmore » m region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μ m band, and on features such as the two-component emission character of this band and the 3 μ m emission plateau.« less

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.

Iron oxide bands in the visible and near-infrared reflectance spectra of primitive asteroids

NASA Technical Reports Server (NTRS)

Jarvis, Kandy S.; Vilas, Faith; Gaffey, Michael J.

1993-01-01

High resolution reflectance spectra of primitive asteroids (C, P, and D class and associated subclasses) have commonly revealed an absorption feature centered at 0.7 microns attributed to an Fe(2+)-Fe(3+) charge transfer transition in iron oxides and/or oxidized iron in phyllosilicates. A smaller feature identified at 0.43 microns has been attributed to an Fe(3+) spin-forbidden transition in iron oxides. In the spectra of the two main-belt primitive asteroids 368 Haidea (D) and 877 Walkure (F), weak absorption features which were centered near the location of 0.60-0.65 microns and 0.80-0.90 microns prompted a search for features at these wavelengths and an attempt to identify their origin(s). The CCD reflectance spectra obtained between 1982-1992 were reviewed for similar absorption features located near these wavelengths. The spectra of asteroids in which these absorption features have been identified are shown. These spectra are plotted in order of increasing heliocentric distance. No division of the asteroids by class has been attempted here (although the absence of these features in the anhydrous S-class asteroids, many of which have presumably undergone full heating and differentiation should be noted). For this study, each spectrum was treated as a continuum with discrete absorption features superimposed on it. For each object, a linear least squares fit to the data points defined a simple linear continuum. The linear continuum was then divided into each spectrum, thus removing the sloped continuum and permitting the intercomparison of residual spectral features.

Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jin; Li, Wenbin; Zhu, Mao

2014-03-15

The localized surface plasmon resonances (LSPRs) of gold particles assembled on a crystal plate are a powerful tool for biological sensors. Here, we prepare gold colloids in different pH solutions. We monitor the effects of the particle radius and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of about 3°) crystal plates supporting gold nanoparticles. The surface morphologies were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis) spectroscopy, and atomic force microscopy (AFM). The results showed that the gold particle coverage decreases with increasing pH value of the gold colloid solution. This phenomenon demonstrates thatmore » self-assembled gold surfaces were formed via the electrostatic adsorption of gold particles on the positively charged, ionized amino groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles with different coverage degree on the crystal plates showed that the LSPR properties are highly dependent on pH.« less

SUT-NANOTEC-SLRI beamline for X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10 8to 2 × 10 10 photons s -1(100 mA) -1varying across photon energies. Details of the beamlinemore » and XAS instrumentation are described. To demonstrate the beamline performance,K-edge XANES spectra of MgO, Al 2O 3, S 8, FeS, FeSO 4, Cu, Cu 2O and CuO, and EXAFS spectra of Cu and CuO are presented.« less

High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

DOE PAGES

Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.; ...

2016-07-01

Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO 2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO 2 is not an ionic compound as previously believed. The Th 6d occupancy in the ground statemore » was estimated to be twice that of the Th 5f states. Here, we demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.« less

Analysis of atmospheric trace constituents from high resolution infrared balloon-borne and ground-based solar absorption spectra

NASA Technical Reports Server (NTRS)

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

1991-01-01

Results of ongoing studies of high-resolution solar absorption spectra aimed at the identification and quantification of trace constituents of importance in the chemistry of the stratosphere and upper troposphere are presented. An analysis of balloon-borne and ground-based spectra obtained at 0.0025/cm covering the 700-2200/cm interval is presented. The 0.0025/cm spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of quantifying trace constituents. Results for COF2, F22, SF6, and other species are presented. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra are also discussed.

Analysis of Shuttle Multispecral Infrared Radiometer measurements of the western Saudi Arabian shield.

USGS Publications Warehouse

Rowan, Lawrence C.; Goetz, Alexander F.H.; Abbott, Elsa

1987-01-01

During the November 12–14, 1981, mission of the space shuttle Columbia, the Shuttle Multispectral Infrared Radiometer (SMIRR) recorded radiances in ten channels along a 100 m wide groundtrack across the western Saudi Arabian shield. The ten channels are located in the 0.5 to 2.4 μm region, with five positioned between 2.0 and 2.40 μm for measuring absorption features that are diagnostic of OH‐bearing and CO3‐bearing">CO3‐bearing minerals. This exceptionally well exposed area consists of late Proterozoic metamorphic, intermediate to silicic intrusive, and interlayered clastic sedimentary and intermediate silicic volcanic rocks that have not been studied previously using SMIRR data. Plots or traces of unnormalized SMIRR channel ratios were examined before field studies to locate areas with high spectral contrast, especially in the 2.0 μm to 2.40 μm channels. Reflectance spectra were measured in the laboratory for rock and soil samples collected in these areas, and the mineralogic causes of the main absorption features were determined using X‐ray diffraction. Laboratory SMIRR spectra were produced by convolving the ten SMIRR filters with the laboratory spectra. Then, normalized SMIRR reflectance spectra were generated along the groundtrack using normalization coefficients calculated for a field sample representing a uniform, low‐spectral contrast area. Field evaluation shows that unnormalized SMIRR ratio traces are useful, even without specific mineralogic information, for distinguishing rocks that are characterized by Al‐OH, Mg‐OH, and/or CO3">CO3">CO3, Fe3+">Fe3+, and Fe2+ absorption features. Analysis of field samples permits suites of minerals causing absorption features to be identified. However, specific mineral identification cannot be achieved consistently using the SMIRR ratio traces or normalized SMIRR spectra, because the Al‐OH and Mg‐OH absorption features can be caused by more than one of the minerals commonly present. The normalized SMIRR spectra are especially useful for identifying subtle Al‐OH and Mg‐OH absorption features that are difficult to identify in the unnormalized ratio traces and for comparing the relative intensities of absorption features. Al‐OH absorption is related to muscovite, smectite, illite, and kaolinite, whereas Mg‐OH absorption is caused by chlorite, amphibole, and biotite. The principal sources of error in using SMIRR spectral measurements for identifying mineral groups along the orbit 27 groundtrack are inaccuracies in field location and lithologic heterogeneity that is not represented adequately by field samples. Calibration errors may account for systematic albedo and absorption intensity differences between calculated laboratory SMIRR spectra and normalized SMIRR spectra. SMIRR instrument noise and atmospheric factors appear to be less important sources of error. However, as higher spectral and spatial resolution systems are developed for mineral identification, radiometric precision and atmospheric factors will become more important.

Growth, spectroscopy and continuous-wave laser performance of Nd3+:LiLu0.65Y0.35F4 crystal

NASA Astrophysics Data System (ADS)

Demesh, M. P.; Kurilchik, S. V.; Gusakova, N. V.; Yasukevich, A. S.; Kisel, V. E.; Nizamutdinov, A. S.; Marisov, M. M.; Aglyamov, R. D.; Korableva, S. L.; Naumov, A. K.; Semashko, V. V.; Kuleshov, N. V.

2018-04-01

A mixed fluoride crystal of LiLu0.65Y0.35F4 doped with Nd3+ ions was grown by the Bridgman-Stockbarger method. Polarized absorption and luminescence spectra as well as luminescence lifetime were measured at room temperature. Emission probabilities, branching ratios and radiative lifetime were studied within the Judd-Ofelt theory and the emission cross section spectra were calculated. Efficient continuous wave laser operation was demonstrated with the crystal. A maximum output power of 7.7 W and slope efficiency of 60% were achieved at 1047 nm for the TEM00 mode.

Role of Quantum Vibrations on the Structural, Electronic, and Optical Properties of 9-Methylguanine.

PubMed

Law, Yu Kay; Hassanali, Ali A

2015-11-05

In this work, we report theoretical predictions of the UV-absorption spectra of 9-methylguanine using time dependent density functional theory (TDDFT). Molecular dynamics simulations of the hydrated DNA base are peformed using an empirical force field, Born-Oppenheimer ab initio molecular dynamics (AIMD), and finally path-integral AIMD to understand the role of the underlying electronic potential, solvation, and nuclear quantum vibrations on the absorption spectra. It is shown that the conformational distributions, including hydrogen bonding interactions, are perturbed by the inclusion of nuclear quantum effects, leading to significant changes in the total charge and dipole fluctuations of the DNA base. The calculated absorption spectra using the different sampling protocols shows that the inclusion of nuclear quantum effects causes a significant broadening and red shift of the spectra bringing it into closer agreement with experiments.

First light with Trident: multi-platform synthetic quasar spectra

NASA Astrophysics Data System (ADS)

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

2017-01-01

Observational efforts to better understand the nature of the intergalactic and circumgalactic media have relied heavily on the information encoded in the absorption line systems of quasar spectra. Numerical simulations of large-scale structure and galaxy evolution are well-suited to explore the properties of those same media owing to the relative ease with which one can access physical quantities from complex, three-dimensional data. However, a difficulty arises when one tries to make direct “apple-to-apples” comparisons between observed spectra and simulated data. In an effort to provide a common language capable of linking theory and observation, we announce the release of Trident. Trident is a publicly available software tool that enables the creation of realistic synthetic absorption spectra from virtually all widely-used hydrodynamics simulation codes. Through user-controlled levels of spectral realism, direct comparisons between simulated and observed data become not only possible, but greatly simplified. We present the methods for extracting artificial quasar sightlines and generating spectra as well as early-stage applications of those spectra to intergalactic and circumgalactic absorption line studies.

Absorption spectroscopy setup for determination of whole human blood and blood-derived materials spectral characteristics

NASA Astrophysics Data System (ADS)

Wróbel, M. S.; Gnyba, M.; Milewska, D.; Mitura, K.; Karpienko, K.

2015-09-01

A dedicated absorption spectroscopy system was set up using tungsten-halogen broadband source, optical fibers, sample holder, and a commercial spectrometer with CCD array. Analysis of noise present in the setup was carried out. Data processing was applied to the absorption spectra to reduce spectral noise, and improve the quality of the spectra and to remove the baseline level. The absorption spectra were measured for whole blood samples, separated components: plasma, saline, washed erythrocytes in saline and human whole blood with biomarkers - biocompatible nanodiamonds (ND). Blood samples had been derived from a number of healthy donors. The results prove a correct setup arrangement, with adequate preprocessing of the data. The results of blood-ND mixtures measurements show no toxic effect on blood cells, which proves the NDs as a potential biocompatible biomarkers.

Detection of absorption lines in the spectra of X-ray bursts from X1608-52

NASA Astrophysics Data System (ADS)

Nakamura, Norio; Inoue, Hajime; Tanaka, Yasuo

X-ray bursts from X 1608-52 were observed with the gas scintillation proportional counters on the Tenma satellite. Absorption features were detected in the spectra of three bursts among 17 bursts observed. These absorption features are consistent with a common absorption line at 4.1 keV. The energy and the properties of the absorption lines of the X 1608-52 bursts are very similar to those observed from the X 1636-53 bursts by Waki et al. (1984). Near equality of the absorption-line energies for X 1636-53 and X 1608-52 would imply that mass and radius of the neutron stars in these two systems are very similar to each other.

High resolution absolute absorption cross sections of the B ̃(1)A'-X ̃(1)A' transition of the CH2OO biradical.

PubMed

Foreman, Elizabeth S; Kapnas, Kara M; Jou, YiTien; Kalinowski, Jarosław; Feng, David; Gerber, R Benny; Murray, Craig

2015-12-28

Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong B ̃(1)A'-X ̃(1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the B ̃(1)A'-X ̃(1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broadband absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.

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.

Collision-Induced Infrared Absorption by Hydrogen-Helium gas mixtures at Thousands of Kelvin

NASA Astrophysics Data System (ADS)

Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

2010-10-01

The interaction-induced absorption by collisional pairs of H2 molecules is an important opacity source in the atmospheres of the outer planets and cool stars ^[1]. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H2--H2, H2--He, and H2--H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin ^[2]. Laboratory measurements of interaction-induced absorption spectra by H2 pairs exist only at room temperature and below. We show that our results reproduce these measurements closely ^[2], so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures ^[2]. [1] L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 [2] Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, ``Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin'', International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201

Studies of Time-Resolved Fluorescence Spectroscopy and Resolved Absorption Spectra of Nucleic Acid Components.

NASA Astrophysics Data System (ADS)

Fu, Yingxian

1993-01-01

There is considerable uncertainty about dynamic aspects of the photophysics of the adenylyl chromophore, stemming from the discordant values reported for the room temperature fluorescence lifetimes (tau_1 = 5 ps, tau_2 = 330 ps for 9MeAde; tau_1 = 290 ps, tau_2 = 4.17 ns for ATP). Spectra reported in conjunction with these lifetimes create difficulties in assignment of emission. To clarify this situation I have investigated the fluorescence decay times and time -resolved emission spectra of adenylyl compounds under a variety of conditions (concentration, pH, solvent) using sub-ns laser excitation at 265 nm together with gated fast sampling (100 ps) detection and signal averaging. Multi -component decays and spectra are observed in aqueous solution. Major slow components (tau = 4.4 +/- 0.2 ns) with emission maxima at 380 nm are found for all components at pH 1.1 and for ATP at pH 4.4. At pH 7 a fast component (<100 ps) predominates. There is no marked evidence for a concentration dependence, the oscillator strengths are 10^ {-3}-10^{-5} and transitions must be classified as weakly forbidden. Single component emission is observed in acetonitrile and ethanol. The UV absorption spectra of biomolecules d(CG) and polyd(GC)cdotpolyd(GC) exhibit the different hypochromic effects due to different interactions between guanosine(G) and cytidine(C) in stacked form. The present work has been carried out to explain this quantitatively. To approach this problem the absorption spectra of G and C have been resolved into gaussian components using the PeakFit program. The absorption spectra (220-310 nm) of d(CG) and polyd(GC)cdotpolyd(GC) have been fitted with gaussian components of G and C (in the order of increasing energy, G1 and G2, and C1, C2 and C3, respectively), and the contribution to both spectra from individual gaussians is estimated in terms of oscillator strengths. The fitting results suggest that the small hypochromism in absorption spectrum of d(CG) may be attributed to the interactions between G1 and C1; the large hypochromism in absorption spectrum of polyd(GC)cdotpolyd(GC) probably originates from the interactions between G1, C1, C2 and C3. The present work has also resolved a series of absorption spectra of cytidyl chromophore in different pH aqueous solution and various solvents. Time-resolved emission spectra of GMP, dCMP and m^5 -dCMP in different pH aqueous solutions have been determined. The results show that pH affects the lifetimes and spectral characteristics of GMP significantly, but does not affect dCMP and m^5-dCMP.

Nonlinear optical spectra having characteristics of Fano interferences in coherently coupled lowest exciton biexciton states in semiconductor quantum dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gotoh, Hideki, E-mail: gotoh.hideki@lab.ntt.co.jp; Sanada, Haruki; Yamaguchi, Hiroshi

2014-10-15

Optical nonlinear effects are examined using a two-color micro-photoluminescence (micro-PL) method in a coherently coupled exciton-biexciton system in a single quantum dot (QD). PL and photoluminescence excitation spectroscopy (PLE) are employed to measure the absorption spectra of the exciton and biexciton states. PLE for Stokes and anti-Stokes PL enables us to clarify the nonlinear optical absorption properties in the lowest exciton and biexciton states. The nonlinear absorption spectra for excitons exhibit asymmetric shapes with peak and dip structures, and provide a distinct contrast to the symmetric dip structures of conventional nonlinear spectra. Theoretical analyses with a density matrix method indicatemore » that the nonlinear spectra are caused not by a simple coherent interaction between the exciton and biexciton states but by coupling effects among exciton, biexciton and continuum states. These results indicate that Fano quantum interference effects appear in exciton-biexciton systems at QDs and offer important insights into their physics.« less

Photoluminescence and gain/absorption spectra of a driven-dissipative electron-hole-photon condensate

NASA Astrophysics Data System (ADS)

Hanai, Ryo; Littlewood, Peter B.; Ohashi, Yoji

2018-06-01

We investigate theoretically nonequilibrium effects on photoluminescence and gain/absorption spectra of a driven-dissipative exciton-polariton condensate, by employing the combined Hartree-Fock-Bogoliubov theory with the generalized random phase approximation extended to the Keldysh formalism. Our calculated photoluminescence spectra is in semiquantitative agreement with experiments, where features such as a blue shift of the emission from the condensate, the appearance of the dispersionless feature of a diffusive Goldstone mode, and the suppression of the dispersive profile of the mode are obtained. We show that the nonequilibrium nature of the exciton-polariton condensate strongly suppresses the visibility of the Bogoliubov dispersion in the negative energy branch (ghost branch) in photoluminescence spectra. We also show that the trace of this branch can be captured as a hole burning effect in gain/absorption spectra. Our results indicate that the nonequilibrium nature of the exciton-polariton condensate strongly reduces quantum depletion, while a scattering channel to the ghost branch is still present.

Excitation spectra of retinal by multiconfiguration pair-density functional theory.

PubMed

Dong, Sijia S; Gagliardi, Laura; Truhlar, Donald G

2018-03-07

Retinal is the chromophore in proteins responsible for vision. The absorption maximum of retinal is sensitive to mutations of the protein. However, it is not easy to predict the absorption spectrum of retinal accurately, and questions remain even after intensive investigation. Retinal poses a challenge for Kohn-Sham density functional theory (KS-DFT) because of the charge transfer character in its excitations, and it poses a challenge for wave function theory because the large size of the molecule makes multiconfigurational perturbation theory methods expensive. In this study, we demonstrate that multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to predict the vertical excitation energies of 11-Z retinal, and it reproduces the experimentally determined absorption band widths and peak positions better than complete active space second-order perturbation theory (CASPT2). The consistency between complete active space self-consistent field (CASSCF) and KS-DFT dipole moments is demonstrated to be a useful criterion in selecting the active space. We also found that the nature of the terminal groups and the conformations of retinal play a significant role in the absorption spectrum. By considering a thermal distribution of conformations, we predict an absorption spectrum of retinal that is consistent with the experimental gas-phase spectrum. The location of the absorption peak and the spectral broadening based on MC-PDFT calculations agree better with experiments than those of CASPT2.

[Preparation and spectral analysis of a new type of blue light-emitting material delta-Alq3].

PubMed

Wang, Hua; Hao, Yu-ying; Gao, Zhi-xiang; Zhou, He-feng; Xu, Bing-she

2006-10-01

In the present article, delta-Alq3, a new type of blue light-emitting material, was synthesized and investigated by IR spectra, XRD spectra, UV-Vis absorption spectra, photoluminescence (PL) spectra, and electroluminescence (EL) spectra. The relationship between molecular spatial structure and spectral characteristics was studied by the spectral analysis of delta-Alq3 and alpha-Alq3. Results show that a new phase of Alq3 (delta-Alq3) can be obtained by vacuum heating alpha-Alq3, and the molecular spatial structure of alpha-Alq3 changes during the vacuum heating. The molecular spatial structure of delta-Alq3 lacks symmetry compared to alpha-Alq3. This transformation can reduce the electron cloud density on phenoxide of Alq3 and weaken the intermolecular conjugated interaction between adjacent Alq3 molecules. Hence, the pi--pi* electron transition absorption peak of delta-Alq3 shifts toward short wavelength in UV-Vis absorption spectra, and the maximum emission peak of delta-Alq3 (lamda max = 480 nm) blue-shifts by 35 nm compared with that of alpha-Alq3 (lamda max = 515 nm) in PL spectra. The maximum emission peaks of delta-Alq3 and alpha-Alq3 are all at 520 nm in EL spectra.

Absorption coefficients of solid NH3 from 50 to 7000 per cm

NASA Technical Reports Server (NTRS)

Sill, G.; Fink, U.; Ferraro, J. R.

1980-01-01

Thin-film spectra of solid NH3 at a resolution of 1 per cm were used to determine its absorption coefficient over the range 50-7000 per cm. The thin films were formed inside a liquid N2 cooled dewar using a variety of substrates and dewar windows. The spectra were recorded with two Fourier spectrometers, one covering the range from 1 to 4 microns and the other from 2.6 to 200 microns. The thickness of the films was measured with a laser interference technique. The absorption coefficients were determined by application of Lambert's law and by a fitting procedure to the observed spectra using thin-film theory. Good agreement was found with the absorption coefficients recently determined by other investigators over a more restricted wavelength range. A metastable phase was observed near a temperature of 90 K and its absorption coefficient is reported. No other major spectral changes with temperature were noted for the range 88-120 K.

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.

Measurement of Absorption Coefficient of Paraformaldehyde and Metaldehyde with Terahertz Spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, J.; Xia, T.; Chen, Q.; Sun, Q.; Deng, Y.; Wang, C.

2018-03-01

The characteristic absorption spectra of paraformaldehyde and metaldehyde in the terahertz frequency region are obtained by terahertz time-domain spectroscopy (THz-TDS). In order to reduce the absorption of terahertz (THz) wave by water vapor in the air and the background noise, the measurement system was filled with dry air and the measurements were conducted at the temperature of 24°C. Meanwhile, the humidity was controlled within 10% RH. The THz frequency domain spectra of samples and their references from 0 to 2.5 THz were analyzed via Fourier transform. The refractive index and absorption coefficients of the two aldehydes were calculated by the model formulas. From 0.1 to 2.5 THz, there appear two weak absorption peaks at 1.20 and 1.66 THz in the absorption spectra of paraformaldehyde. Only one distinct absorption peak emerges at 1.83 THz for metaldehyde. There are significant differences between the terahertz absorption coefficients of paraformaldehyde and metaldehyde, which can be used as "fingerprints" to identify these substances. Furthermore, the relationship between the average absorption coefficients and mass concentrations was investigated and the average absorption coefficient-mass concentration diagrams of paraformaldehyde and metaldehyde were shown. For paraformaldehyde, there is a linear relationship between the average absorption coefficient and the natural logarithm of mass concentration. For metaldehyde, there exists a simpler linear relationship between the average absorption coefficient and the mass concentration. Because of the characteristics of THz absorption of paraformaldehyde and metaldehyde, the THz-TDS can be applied to the qualitative and quantitative detection of the two aldehydes to reduce the unpredictable hazards due to these substances.

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

PubMed Central

Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng

2018-01-01

Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively. PMID:29657794

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

PubMed

Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing

2018-03-01

Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.

Infrared reflectance spectra: Effects of particle size, provenance and preparation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Yin-Fong; Myers, Tanya L.; Brauer, Carolyn S.

2014-09-22

We have recently developed methods for making more accurate infrared total and diffuse directional - hemispherical reflectance measurements using an integrating sphere. We have found that reflectance spectra of solids, especially powders, are influenced by a number of factors including the sample preparation method, the particle size and morphology, as well as the sample origin. On a quantitative basis we have investigated some of these parameters and the effects they have on reflectance spectra, particularly in the longwave infrared. In the IR the spectral features may be observed as either maxima or minima: In general, upward-going peaks in the reflectancemore » spectrum result from strong surface scattering, i.e. rays that are reflected from the surface without bulk penetration, whereas downward-going peaks are due to either absorption or volume scattering, i.e. rays that have penetrated or refracted into the sample interior and are not reflected. The light signals reflected from solids usually encompass all such effects, but with strong dependencies on particle size and preparation. This paper measures the reflectance spectra in the 1.3 – 16 micron range for various bulk materials that have a combination of strong and weak absorption bands in order to observe the effects on the spectral features: Bulk materials were ground with a mortar and pestle and sieved to separate the samples into various size fractions between 5 and 500 microns. The median particle size is demonstrated to have large effects on the reflectance spectra. For certain minerals we also observe significant spectral change depending on the geologic origin of the sample. All three such effects (particle size, preparation and provenance) result in substantial change in the reflectance spectra for solid materials; successful identification algorithms will require sufficient flexibility to account for these parameters.« less

Infrared reflectance spectra: effects of particle size, provenance and preparation

NASA Astrophysics Data System (ADS)

Su, Yin-Fong; Myers, Tanya L.; Brauer, Carolyn S.; Blake, Thomas A.; Forland, Brenda M.; Szecsody, J. E.; Johnson, Timothy J.

2014-10-01

We have recently developed methods for making more accurate infrared total and diffuse directional - hemispherical reflectance measurements using an integrating sphere. We have found that reflectance spectra of solids, especially powders, are influenced by a number of factors including the sample preparation method, the particle size and morphology, as well as the sample origin. On a quantitative basis we have investigated some of these parameters and the effects they have on reflectance spectra, particularly in the longwave infrared. In the IR the spectral features may be observed as either maxima or minima: In general, upward-going peaks in the reflectance spectrum result from strong surface scattering, i.e. rays that are reflected from the surface without bulk penetration, whereas downward-going peaks are due to either absorption or volume scattering, i.e. rays that have penetrated or refracted into the sample interior and are not reflected. The light signals reflected from solids usually encompass all such effects, but with strong dependencies on particle size and preparation. This paper measures the reflectance spectra in the 1.3 - 16 micron range for various bulk materials that have a combination of strong and weak absorption bands in order to observe the effects on the spectral features: Bulk materials were ground with a mortar and pestle and sieved to separate the samples into various size fractions between 5 and 500 microns. The median particle size is demonstrated to have large effects on the reflectance spectra. For certain minerals we also observe significant spectral change depending on the geologic origin of the sample. All three such effects (particle size, preparation and provenance) result in substantial change in the reflectance spectra for solid materials; successful identification algorithms will require sufficient flexibility to account for these parameters.

FSFE: Fake Spectra Flux Extractor

NASA Astrophysics Data System (ADS)

Bird, Simeon

2017-10-01

The fake spectra flux extractor generates simulated quasar absorption spectra from a particle or adaptive mesh-based hydrodynamic simulation. It is implemented as a python module. It can produce both hydrogen and metal line spectra, if the simulation includes metals. The cloudy table for metal ionization fractions is included. Unlike earlier spectral generation codes, it produces absorption from each particle close to the sight-line individually, rather than first producing an average density in each spectral pixel, thus substantially preserving more of the small-scale velocity structure of the gas. The code supports both Gadget (ascl:0003.001) and AREPO.

The manifestation of optical centers in UV-Vis absorption and luminescence spectra of white blood human cells

NASA Astrophysics Data System (ADS)

Terent'yeva, Yu G.; Yashchuk, V. M.; Zaika, L. A.; Snitserova, O. M.; Losytsky, M. Yu

2016-12-01

A white blood human cells spectral investigation is presented. The aim of this series of experiments was to obtain and analyze the absorption and luminescence (fluorescence and phosphorescence) spectra at room temperature and at 78 K of newly isolated white blood human cells and their organelles. As a result the optical centers and possible biochemical components that form the studied spectra where identified. Also the differences between the spectra of abnormal cells (B-cell chronic lymphocytic leukemia BCLL) and normal ones were studied for the whole cells and individual organelles.

Study of the absorption spectra of Fricke Xylenol Orange gel dosimeters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gambarini, Grazia; Artuso, Emanuele; Liosi, Giulia Maria

2015-07-01

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

Effect of in-material losses on terahertz absorption, transmission, and reflection in photonic crystals made of polar dielectrics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serebryannikov, Andriy E., E-mail: andser@amu.edu.pl; Nanotechnology Research Center—NANOTAM, Bilkent University, 06800 Ankara; Nojima, S.

2015-10-07

The effect of the material absorption factor on terahertz absorption (A), transmittance (T), and reflectance (R) for slabs of PhC that comprise rods made of GaAs, a polar dielectric, is studied. The main goal was to illustrate how critical a choice of the absorption factor for simulations is and to indicate the importance of the possible modification of the absorption ability by using either active or lossy impurities. The spectra of A, T, and R are strongly sensitive to the location of the polaritonic gap with respect to the photonic pass and stop bands connected with periodicity that enables themore » efficient combination of the effects of material and structural parameters. It will be shown that the spectra can strongly depend on the utilized value of the material absorption factor. In particular, both narrow and wide absorption bands may appear owing to a variation of the material parameters with a frequency in the vicinity of the polaritonic gap. The latter are often achieved at wideband suppression of transmission, so that an ultra-wide stop band can appear as a result of adjustment of the stop bands having different origin. The results obtained at simultaneous variation of the absorption factor and frequency, and angle of incidence and frequency, indicate the possibility of the existence of wide ranges of tolerance, in which the basic features do remain. This allows for mitigating the accuracy requirements for the absorption factor in simulations and promises the efficient absorption of nonmonochromatic waves and beams with a wide angular spectrum. Suppression of narrowband effects in transmission is demonstrated at rather large values of the absorption factor, when they appear due to either the defect modes related to structural defects or dispersion inspired variations of the material parameters in the vicinity of the polaritonic gap. Comparison with auxiliary structures helps one to detect the common features and differences of homogeneous slabs and slabs of a PhC, which are made of GaAs.« less

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.

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

DTIC Science & Technology

2015-05-21

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

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

The far-ultraviolet spectra and geometric albedos of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Clarke, J. T.; Moos, H. W.; Feldman, P. D.

1982-01-01

Spectra and geometric albedoes in the range 1200 to 1940 A are compiled for Jupiter and Saturn on the basis of IUE observations. The spectra of both planets are dominated by H Lyman-alpha emission line at 1216 A, although absorption bands of C2H2 are apparent at longer wavelengths, particularly in the spectrum of Saturn, and the C I line at 1657 A is also observed. Geometric albedoes show emission features corresponding to the weak H2 Lyman and Werner bands around 1230-1280 A, auroral Lyman band emission, C I emission, and C2H2 absorption from 1600 to 1900 A. A model of atmospheric absorption in homogeneously mixed atmospheres of H2 and trace molecular absorbers is then presented and fit to the Jupiter albedo, resulting in a predicted atmosphere containing C2H2 and an unidentified molecular or particulate absorber. Finally, north-south maps of Jupiter continuum emission show limb darkening, and a comparison of equatorial and polar spectra indicates a polar increase in C2H2 absorption and weaker polar H2 emissions than previously reported.

Absorption and emission spectra of Li atoms trapped in rare gas matrices

NASA Astrophysics Data System (ADS)

Wright, J. J.; Balling, L. C.

1980-10-01

Pulsed-dye-laser excitation has been used to investigate the optical absorption and emission spectra of Li atoms trapped in Ar, Kr, and Xe matrices at 10 °K. Attempts to stabilize Li atoms in a Ne matrix at 2 °K were unsuccessful. Results for all three rare gases were qualitatively the same. White light absorption scans showed a single absorption with three peaks centered near the free-atom 2s→2p transition wavelength. The intensity of fluorescence produced by dye-laser excitation within this absorption band was measured as a function of emission wavelength. Excitation of the longest- and shortest-wavelength absorption peaks produced identical emission profiles, but no distinct fluorescence signal was detected when the laser was tuned to the central absorption peaks, indicating that the apparent absorption triplet is actually the superposition of a singlet and a doublet absorption originating from two different trapping sites. No additional absorption bands were detected.

Integration of Ground-Based Solar FT-IR Absorption Spectroscopy and Open-Path Systems for Atmospheric Analysis

NASA Astrophysics Data System (ADS)

Steill, J. D.; Hager, J. S.; Compton, R. N.

2006-05-01

Air quality issues in the Knoxville and East Tennessee region are of great concern, particularly as regards the nearby Great Smoky Mountains National Park. Infrared absorption spectroscopy of the atmosphere provides a unique opportunity to analyze the local chemical composition, since many trace atmospheric constituents are open to this analysis, such as O3, CO, CH4, and N2O. Integration of a Bomem DA8 FT-IR spectrometer with rooftop sun-tracking optics and an open-path system provide solar-sourced and boundary- layer atmospheric infrared spectra of these and other relevant atmospheric components. Boundary layer concentrations as well as total column abundances and vertical concentration profiles are derived. Vertical concentration profiles are determined by fitting solar-sourced absorbance lines with the SFIT2 algorithm. Improved fitting of solar spectra has been demonstrated by incorporating the tropospheric concentrations as determined by open-path measurements. A record of solar-sourced atmospheric spectra of greater than two years duration is under analysis to characterize experimental error and thus the limit of precision in the concentration determinations. Initial efforts using atmospheric O2 as a calibration indicate the solar- sourced spectra may not yet meet the precision required for accurate atmospheric CO2 quantification by such efforts as the OCO and NDSC. However, this variability is also indicative of local concentration fluxes pertinent to the regional atmospheric chemistry. In addition to providing a means to improve the analysis of solar spectra, the open-path data is useful for elucidation of seasonal and diurnal trends in the local trace gas concentrations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marron, A.C.

Middle ultraviolet spectra of the atmospheric airglow were obtained from a March 1992 rocket flight of the NPS MUSTANG instrument. These spectra are analyzed from 1900 A to 3100 A, over an altitude range of 100 km to 320 km. The data are modeled with computer generated synthetic spectra for the following emissions: N2 Vegard Kaplan (VK); N2 Lyman-Birge-Hopfield (LBH); and NO Gamma, Delta, and Epsilon bands. A best fit procedure was developed. The resulting synthetic spectra agree well with obtained airglow data. Confirmation was made of the theoretical self absorption versus non-self absorption processes of the NO (0,0), (1,0),more » (2,0) gamma resonance band emissions. NO self absorption is a necessary inclusion of any atmospheric nitric oxide analysis stratagem. Profiles of temperature versus altitude and NO column density versus altitude for the rocket flight are estimated. Airglow, Ionosphere, Ultraviolet spectroscopy.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vidmer, Alexandre, E-mail: alexandre@vidmer.com; Sclauzero, Gabriele; Pasquarello, Alfredo

The infrared absorption spectra of jennite, tobermorite 14 Å, anomalous tobermorite 11 Å, and normal tobermorite 11 Å are simulated within a density-functional-theory scheme. The atomic coordinates and the cell parameters are optimized resulting in structures which agree with previous studies. The vibrational frequencies and modes are obtained for each mineral. The vibrational density of states is analyzed through extensive projections on silicon tetrahedra, oxygen atoms, OH groups, and water molecules. The coupling with the electric field is achieved through the use of density functional perturbation theory, which yields Born effective charges and dielectric constants. The simulated absorption spectra reproducemore » well the experimental spectra, thereby allowing for a detailed interpretation of the spectral features in terms of the underlying vibrational modes. In the far-infrared part of the absorption spectra, the interplay between Ca and Si related vibrations leads to differences which are sensitive to the calcium/silicon ratio of the mineral.« less

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

The low-iron, reduced surface of Mercury as seen in spectral reflectance by MESSENGER

NASA Astrophysics Data System (ADS)

Izenberg, Noam R.; Klima, Rachel L.; Murchie, Scott L.; Blewett, David T.; Holsclaw, Gregory M.; McClintock, William E.; Malaret, Erick; Mauceri, Calogero; Vilas, Faith; Sprague, Ann L.; Helbert, Jörn; Domingue, Deborah L.; Head, James W.; Goudge, Timothy A.; Solomon, Sean C.; Hibbitts, Charles A.; Dyar, M. Darby

2014-01-01

The MESSENGER spacecraft's Mercury Atmospheric and Surface Composition Spectrometer (MASCS) obtained more than 1.6 million reflectance spectra of Mercury's surface from near-ultraviolet to near-infrared wavelengths during the first year of orbital operations. A global analysis of spectra in the wavelength range 300-1450 nm shows little regional variation in absolute reflectance or spectral slopes and a lack of mineralogically diagnostic absorptions. In particular, reflectance spectra show no clear evidence for an absorption band centered near 1 μm that would be associated with the presence of ferrous iron in silicates. There is, however, evidence for an ultraviolet absorption possibly consistent with a very low iron content (2-3 wt% FeO or less) in surface silicates and for the presence of small amounts of metallic iron or other opaque minerals in the form of nano- or micrometer-sized particles. These findings are consistent with MESSENGER X-ray and gamma-ray measurements of Mercury's surface iron abundance. Although X-ray and gamma-ray observations indicate higher than expected quantities of sulfur on the surface, reflectance spectra show no absorption bands diagnostic of sulfide minerals. Whereas there is strong evidence of water ice in permanently shadowed craters near Mercury's poles, MASCS spectra provide no evidence for hydroxylated materials near permanently shadowed craters.

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

Measurements of near-IR water vapor absorption at high pressure and temperature

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Liu, X.; Li, H.; Jeffries, J. B.; Hanson, R. K.

2007-03-01

Tunable diode lasers (TDLs) are used to measure high resolution (0.1 cm-1), near-infrared (NIR) water vapor absorption spectra at 700 K and pressures up to 30 atm within a high-pressure and -temperature optical cell in a high-uniformity tube furnace. Both direct absorption and wavelength modulation with second harmonic detection (WMS-2f) spectra are obtained for 6 cm-1 regions near 7204 cm-1 and 7435 cm-1. Direct absorption measurements at 700 K and 10 atm are compared with simulations using spectral parameters from HITRAN and a hybrid database combining HITRAN with measured spectral constants for transitions in the two target spectral regions. The hybrid database reduces RMS error between the simulation and the measurements by 45% for the 7204 cm-1 region and 28% for the 7435 cm-1 region. At pressures above 10 atm, the breakdown of the impact approximation inherent to the Lorentzian line shape model becomes apparent in the direct absorption spectra, and measured results are in agreement with model results and trends at elevated temperatures reported in the literature. The wavelength-modulation spectra are shown to be less affected by the breakdown of the impact approximation and measurements agree well with the hybrid database predictions to higher pressures (30 atm).

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Far Ultraviolet Spectroscopy of Saturn's Icy Moon Rhea

NASA Astrophysics Data System (ADS)

Elowitz, Mark; Hendrix, Amanda; Mason, Nigel J.; Sivaraman, Bhalamurugan

2018-01-01

We present an analysis of spatially resolved, far-UV reflectance spectra of Saturn’s icy satellite Rhea, collected by the Cassini Ultraviolet Imaging Spectrograph (UVIS). In recent years ultraviolet spectroscopy has become an important tool for analysing the icy satellites of the outer solar system (1Hendrix & Hansen, 2008). Far-UV spectroscopy provides unique information about the molecular structure and electronic transitions of chemical species. Many molecules that are suspected to be present in the icy surfaces of moons in the outer solar system have broad absorption features due to electronic transitions that occur in the far-UV portion of the spectrum. The studies show that Rhea, like the other icy satellites of the Saturnian system are dominated by water-ice as evident by the 165-nm absorption edge, with minor UV absorbing contaminants. Far-UV spectra of several Saturnian icy satellites, including Rhea and Dione, show an unexplained weak absorption feature centered near 184 nm. To carry out the geochemical survey of Rhea’s surface, the UVIS observations are compared with vacuum-UV spectra of thin-ice samples measured in laboratory experiments. Thin film laboratory spectra of water-ice and other molecular compounds in the solid phase were collected at near-vacuum conditions and temperatures identical to those at the surface of Rhea. Comparison between the observed far-UV spectra of Rhea’s surface ice and modelled spectra based on laboratory absorption measurements of different non-water-ice compounds show that two possible chemical compounds could explain the 184-nm absorption feature. The two molecular compounds include simple chlorine molecules and hydrazine monohydrate. Attempts to explain the source(s) of these compounds on Rhea and the scientific implications of their possible discovery will be summarized.[1] Hendrix, A. R. & Hansen, C. J. (2008). Icarus, 193, pp. 323-333.

Search for volatiles on icy satellites. I. Europa

USGS Publications Warehouse

Brown, R.H.; Cruikshank, D.P.; Tokunaga, A.T.; Smith, R.G.; Clark, R.N.

1988-01-01

New reflectance spectra have been obtained for both the leading and trailing sides of Europa, using the Cooled Grating Array Spectrometer (CGAS) of the NASA Infrared Telescope Facility (IRTF). The spectra are of higher precision than any yet obtained. Spectra of Europa's trailing side (central meridian longitude ???300??) obtained in 1985 show two weak absorptions near 2.2 and 2.3 ??m. Both of these features as well as others are seen in spectra obtained by R. N. Clark, R. B. Singer, P. D. Owensby, and F.P. Fanale (1980a, Bull. Amer. Astron. Soc. 12, 713-714) at similar central meridian longitude. Data obtained with an improved detector array in 1986, however, do not show the absorptions seen in the 1980 and 1985 spectra. It is not clear why the newest data do not show the apparent absorptions seen in previous years, but the suggestion is that either the 1980 and 1985 data are spurious or that the material responsible for the weak absorptions is no longer detectable. Analysis of the 1980 and 1985 data did not reveal any obvious source of systematic error capable of introducing spurious features, but we are skeptical of any explanation that cites transient deposition, movement, and/or destruction of material on Europa's trailing side to account for the nondetection of the features in the 1986 data. If the weak absorptions seen in the 1980 and 1985 data are real, they can be interpreted as indicating the transient spectroscopic presence of a molecular component on Europa's trailing side different from the water ice that is known to be the dominant surface constituent. Further monitoring is required to determine if the apparent absorptions are real. ?? 1988.

Assessing pearl quality using reflectance UV-Vis spectroscopy: does the same donor produce consistent pearl quality?

PubMed

Mamangkey, Noldy Gustaf F; Agatonovic, Snezana; Southgate, Paul C

2010-09-20

Two groups of commercial quality ("acceptable") pearls produced using two donors, and a group of "acceptable" pearls from other donors were analyzed using reflectance UV-Vis spectrophotometry. Three pearls with different colors produced by the same donor showed different absorption spectra. Cream and gold colored pearls showed a wide absorption from 320 to about 460 nm, while there was just slight reflectance around 400 nm by the white pearl with a pink overtone. Cream and gold pearls reached a reflectance peak at 560 to 590 nm, while the white pearl with pink overtone showed slightly wider absorption in this region. Both cream and gold pearls showed an absorption peak after the reflectance peak, at about 700 nm for the cream pearl and 750 nm for the gold pearl. Two other pearls produced by the same donor (white with cream overtone and cream with various overtones) showed similar spectra, which differed in their intensity. One of these pearls had very high lustre and its spectrum showed a much higher percentage reflectance than the second pearl with inferior lustre. This result may indicate that reflectance is a useful quantitative indicator of pearl lustre. The spectra of two white pearls resulting from different donors with the same color nacre (silver) showed a reflectance at 260 nm, followed by absorption at 280 nm and another reflectance peak at 340 nm. After this peak the spectra for these pearls remained flat until a slight absorption peak around 700 nm. Throughout the visible region, all white pearls used in this study showed similar reflectance spectra although there were differences in reflectance intensity. Unlike the spectral results from white pearls, the results from yellow and gold pearls varied according to color saturation of the pearl. The results of this study show that similarities between absorption and reflectance spectra of cultured pearls resulting from the same saibo donor are negligible and could not be detected with UV-Vis spectrophotometry. Nevertheless, this technique could have a role to play in developing less subjective methods of assessing pearl quality and in further studies of the relationships between pearl quality and that of the donor and recipient oysters.

Composition and structure of fresh ammonia clouds on Jupiter based on quantitative analysis of Galileo/NIMS and New Horizons/LEISA spectra

NASA Astrophysics Data System (ADS)

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

2018-06-01

Ammonia gas has long been assumed to be the main source of condensables for the upper cloud layer on Jupiter, but distinctive spectral features associated with ammonia have been seen only rarely. Since both ammonia and NH4SH absorb in the 3 μm region, and widespread absorption in the 3 μm region was present (Sromovsky and Fry, 2010), identification of the 2 μm absorption feature of NH3 provided an opportunity to clearly establish its presence in Jovian clouds. Baines et al. (2002) succeeded in finding in Near Infrared Mapping Spectrometer (NIMS) observations one feature that had both 2 μm and 3 μm absorption, and many which were known to have absorption at 2.73 μm. They named these Spectrally Identifiable Ammonia Clouds (SIACs). They also argued that these were fresh ammonia clouds that would eventually succumb to some process that would obscure their absorption features. Detection of many more of the 2 μm features was later achieved by New Horizon's Linear Etalon Imaging Spectral Array (LEISA) instrument, which provided both the spatial and spectral resolution needed to identify these features. Here we report on the first quantitative modeling that uses NIMS spectra over a broad (1-5.2 μm) spectral range and LEISA spectra over a much narrower (1.25-2.5 μm) spectral range to constrain the cloud structure and composition of these rare cloud features and compare them to background clouds. We find that the absorption signature at 2 μm, which is well characterized in LEISA spectra, is relatively subtle and easily matched by model clouds containing spherical particles of ammonia ice with radii of 2-4 μm. The NIMS spectra, which cover both reflected sunlight as well as thermal emission regions are more difficult to model with cloud materials plausibly present in Jupiter's atmosphere. The best signal/noise spectra obtained from NIMS provide a relatively sparse sampling of the spectrum, which does not establish the detailed shape of the 3 μm absorption region. NIMS SIAC spectra with much denser spectral sampling are limited by much higher noise levels that degrade the features that are key to identifying cloud composition. The structure which best matches the wide range NIMS SIAC spectra contains two overlapping NH3 clouds with a bi-modal size distribution over an optically thick NH4SH cloud. The bi-modal distribution may be a result of modeling non-spherical, possibly fractal aggregate, particles with spheres.

AKARI observations of brown dwarfs. IV. Effect of elemental abundances on near-infrared spectra between 1.0 and 5.0 μm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sorahana, S.; Yamamura, I.

2014-09-20

The detection of the CO{sub 2} absorption band at 4.2 μm in brown dwarf spectra by AKARI has made it possible to discuss CO{sub 2} molecular abundance in brown dwarf atmospheres. In our previous studies, we found an excess in the 4.2 μm CO{sub 2} absorption band of three brown dwarf spectra, and suggested that these deviations were caused by high C and O elemental abundances in their atmospheres. To validate this hypothesis, we have constructed a set of models of brown dwarf atmospheres with various elemental abundance patterns, and we investigate the variations of the molecular composition and themore » thermal structure, and how they affect the near-infrared spectra between 1.0 and 5.0 μm. The 4.2 μm CO{sub 2} absorption band in some late-L and T dwarfs taken by AKARI is stronger or weaker than predicted by corresponding models with solar abundance. By comparing the CO{sub 2} band in the model spectra to the observed near-infrared spectra, we confirm possible elemental abundance variations among brown dwarfs. We find that the band strength is especially sensitive to O abundance, but C is also needed to reproduce the entire near-infrared spectra. This result indicates that both the C and O abundances should increase and decrease simultaneously for brown dwarfs. We find that a weaker CO{sub 2} absorption band in a spectrum can also be explained by a model with lower 'C and O' abundances.« less

UV-Visible Spectra of PAHs and Derivatives Seeded in Supersonic Jet. Astrophysical Implications

NASA Astrophysics Data System (ADS)

Salma, Bejaoui; Salama, Farid

2018-06-01

Laboratory absorption spectra of Polycyclic Aromatic Hydrocarbons (PAHs) and PAH derivatives measured under astrophysical relevant conditions are crucial to test the PAHs-DIBs hypothesis as well as the PAH model for the IR emission bands. Our dedicated experimental setup on the COsmic SImulation Chamber (COSmIC) provides an excellent platform to study neutral and ionized PAHs under the low temperature and pressure conditions that are representative of interstellar environments [1]. In this work, we study the effect of the substitution of CH bond(s) by a nitrogen atom(s) on the electronic spectra of phenanthrene. The electronic transitions associated with the lower excited states of neutral phenanthrene (C14H10) and phenanthridine (C13H9N) are measured in gas phase in the 315-345 nm region. Molecules are seeded in a supersonic expansion of argon gas and the absorption spectra are measured using the Cavity Ring Down Spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of phenanthrene, phenantridine and 1,10-phenanthroline (C12H8N2) isolated in 10 K argon matrices are also performed. The comparison between the CRDS spectra with the absorption of the matrix-isolated molecules highlight the matrix-induced perturbations in band position, profiles and broadening and illustrates the need of gas phase measurements for more accurate comparisons with astronomical spectra.[1] Salama, F., Galazutdinov, G., Krelowski, et al. ApJ 728, 154[FS1] (2011).[2] A. Tielens, ApJ 526 Pt 1265–273 (2008),Acknowledgements: This research is supported by the APRA Program of NASA SMD

Uranus' post-equinox north polar brightening characterized with 2013 and 2016 IRTF SpeX observation

NASA Astrophysics Data System (ADS)

Fry, Patrick M.; Sromovsky, Lawrence A.

2017-10-01

Since its 2007 equinox, the atmosphere of Uranus, as seen in the near infrared (~800-1600 nm) has exhibited dramatic changes. Its southern polar cap, prominent prior to equinox, has faded and a similar polar cap has begun developing in the north. Karkoschka and Tomasko (2009, Icarus 202:287) demonstrated that in 2002 the south polar region, brighter than lower latitude regions when viewed at wavelengths of intermediate methane absorption, was depleted in methane compared to darker regions. Tice et al. (2013, Icarus 223:684) and Sromovsky et al. (2014, Icarus 238:137) concluded that the northern polar regions were similarly depleted. The north polar region (45N-90N) has continued to brighten; modeling of 2015 HST STIS observations (Fry et al. 2016, AAS DPS #48 421.03) suggested that the latitudinal methane distribution has remained essentially unchanged since equinox, but brightening from 2012 to 2015 was due to changes in aerosol scattering. We acquired 0.8-2.5 μm SpeX spectra in 2013 (central meridian) and 2016 (pole-aligned spectra at 0, 0.4, 0.8, and 1.2 arcsec. distant from the CM) under similar seeing conditions (0.4-0.5 arcsec.). The SpeX wavelength range gives us an additional wavelength region where H2 absorption competes with or exceeds CH4 absorption, and a wider wavelength range to characterize aerosol particle properties, compared to STIS. The multiple spectra in 2016 allow us to compare specific latitudes to 2013 at the same view angles (and to use center-to-limb constraints in modeling 2016 spectra). We will present observations, reduction procedures, comparative (2013 vs 2016) modeling of latitudinal methane abundance and vertical aerosol profiles, and compare to 2012/2015 STIS analysis. Preliminary analysis shows that lower latitudes (~30N) have not changed since 2013, but higher latitudes (~70N) have undergone continued significant brightening at pseudo-continuum wavelengths dominated by both H2 (1080 nm, up ~50%) and CH4 (1290 nm, also up ~50%) absorption , indicating a change in scattering properties.This work is supported by NASA Solar System Observations grant NNA16AH99G.

Recent advances in collisional effects on spectra of molecular gases and their practical consequences

NASA Astrophysics Data System (ADS)

Hartmann, Jean-Michel; Tran, Ha; Armante, Raymond; Boulet, Christian; Campargue, Alain; Forget, François; Gianfrani, Livio; Gordon, Iouli; Guerlet, Sandrine; Gustafsson, Magnus; Hodges, Joseph T.; Kassi, Samir; Lisak, Daniel; Thibault, Franck; Toon, Geoffrey C.

2018-07-01

We review progress, since publication of the book ``Collisional effects on molecular spectra: Laboratory experiments and models, consequences for applications" (Elsevier, Amsterdam, 2008), on measuring, modeling and predicting the influence of pressure (ie of intermolecular collisions) on the spectra of gas molecules. We first introduce recently developed experimental techniques of high accuracy and sensitivity. We then complement the aforementioned book by presenting the theoretical approaches, results and data proposed (mostly) in the last decade on the topics of isolated line shapes, line-broadening and -shifting, line-mixing, the far wings and associated continua, and collision-induced absorption. Examples of recently demonstrated consequences of the progress in the description of spectral shapes for some practical applications (metrology, probing of gas media, climate predictions) are then given. Remaining issues and directions for future research are finally discussed.

Quantitative imaging of bilirubin by photoacoustic microscopy

NASA Astrophysics Data System (ADS)

Zhou, Yong; Zhang, Chi; Yao, Da-Kang; Wang, Lihong V.

2013-03-01

Noninvasive detection of both bilirubin concentration and its distribution is important for disease diagnosis. Here we implemented photoacoustic microscopy (PAM) to detect bilirubin distribution. We first demonstrate that our PAM system can measure the absorption spectra of bilirubin and blood. We also image bilirubin distributions in tissuemimicking samples, both without and with blood mixed. Our results show that PAM has the potential to quantitatively image bilirubin in vivo for clinical applications.

Hydrogen peroxide on the surface of Europa

USGS Publications Warehouse

Carlson, R.W.; Anderson, M.S.; Johnson, R.E.; Smythe, W.D.; Hendrix, A.R.; Barth, C.A.; Soderblom, L.A.; Hansen, G.B.; McCord, T.B.; Dalton, J.B.; Clark, R.N.; Shirley, J.H.; Ocampo, A.C.; Matson, D.L.

1999-01-01

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Hydrogen peroxide on the surface of Europa.

PubMed

Carlson, R W; Anderson, M S; Johnson, R E; Smythe, W D; Hendrix, A R; Barth, C A; Soderblom, L A; Hansen, G B; McCord, T B; Dalton, J B; Clark, R N; Shirley, J H; Ocampo, A C; Matson, D L

1999-03-26

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Artificial neural networks for retrieving absorption and reduced scattering spectra from frequency-domain diffuse reflectance spectroscopy at short source-detector separation

PubMed Central

Chen, Yu-Wen; Chen, Chien-Chih; Huang, Po-Jung; Tseng, Sheng-Hao

2016-01-01

Diffuse reflectance spectroscopy (DRS) based on the frequency-domain (FD) technique has been employed to investigate the optical properties of deep tissues such as breast and brain using source to detector separation up to 40 mm. Due to the modeling and system limitations, efficient and precise determination of turbid sample optical properties from the FD diffuse reflectance acquired at a source-detector separation (SDS) of around 1 mm has not been demonstrated. In this study, we revealed that at SDS of 1 mm, acquiring FD diffuse reflectance at multiple frequencies is necessary for alleviating the influence of inevitable measurement uncertainty on the optical property recovery accuracy. Furthermore, we developed artificial neural networks (ANNs) trained by Monte Carlo simulation generated databases that were capable of efficiently determining FD reflectance at multiple frequencies. The ANNs could work in conjunction with a least-square optimization algorithm to rapidly (within 1 second), accurately (within 10%) quantify the sample optical properties from FD reflectance measured at SDS of 1 mm. In addition, we demonstrated that incorporating the steady-state apparatus into the FD DRS system with 1 mm SDS would enable obtaining broadband absorption and reduced scattering spectra of turbid samples in the wavelength range from 650 to 1000 nm. PMID:27446671

Comparison of visible and near-infrared reflectance spectra of CM2 carbonaceous chondrites and primitive asteroids

NASA Technical Reports Server (NTRS)

Vilas, F.; Hiroi, T.; Zolensky, M. E.

1993-01-01

Spectra of primitive asteroids (defined as C, P, and D classes and associated subclasses) were compared to the limited number of spectra of CM2 carbonaceous chondrites. An absorption feature located at 0.7 microns attributed to an Fe(+2) - Fe(+3) charge transfer absorption in iron oxides in phyllosilicates is apparent in some of the CM2 carbonaceous chondrite spectra and many of the asteroid spectra. Sawyer found a correlation between the area of the 0.7 micron feature and the mean semimajor axis of the asteroids. Spectra of a larger sample of carbonaceous chondrites, including 7 CM2 chondrites, covering a spectral interval of 0.30-2.5 microns were recently obtained using the Relab instrument at Brown University. These spectra were compared with spectrophotometric asteroid observations in a separate abstract. Those spectra of CM2 chondrites were isolated into the UV, visible and near-infrared spectral regions in order to compare them with high-quality narrowband reflectance spectra.

Optical characteristics of butyl rubber loaded with general purpose furnace (GPF) carbon black

NASA Astrophysics Data System (ADS)

Alfaramawi, K.

2018-06-01

Optical characteristics of butyl rubber/GPF carbon black (BR/GPFCB) composites with carbon black (CB) concentrations 40, 60, 80 and 100 phr (part per hundred part of rubber) were investigated. The structure of the BR/GPFCB composites was analyzed by x-ray diffraction (XRD). All samples with various CB showed diffraction peaks around 2θ = 14°, 25° and 44° which correspond to interlayer spacing of 6.23 Å, 3.62 Å and 2.10 Å respectively. The peaks were shifted toward larger 2θ angles with increasing CB concentration, indicating a decrease in layer spacing. Ultraviolet and visible (UV–vis) absorbance spectra in the range from 200 nm to 800 nm of the BR/GPFCB composites were studied. In the UV range of the spectra, an absorption edge was recorded. Direct and indirect optical band gaps for the composites were evaluated. The direct band gap values were found-as shown to be slightly greater than that of the indirect ones. The reflectance spectra in the UV optical range were demonstrated. Most of the incident UV light was absorbed inside the composites while a very small fraction was reflected and transmitted. This was attributed to the high UV absorption property of the CB filler. The refractive index of the composite was calculated from the reflectance data. The dependence of the real and imaginary parts of the complex dielectric constant on the incident light energy was characterized. The dielectric loss factor was found to decrease with increasing incident photon energy until approximately 5.5 eV (around the absorption edge) and then it increased rapidly.

Randic and Schultz molecular topological indices and their correlation with some X-ray absorption parameters

NASA Astrophysics Data System (ADS)

Khatri, Sunil; Kekre, Pravin A.; Mishra, Ashutosh

2016-10-01

The properties of a molecular system are affected by the topology of molecule. Therefore many studies have been made where the various physic-chemical properties are correlated with the topological indices. These studies have shown a very good correlation demonstrating the utility of the graph theoretical approach. It is, therefore, very natural to expect that the various physical properties obtained by the X-ray absorption spectra may also show correlation with the topological indices. Some complexes were used to establish correlation between topological indices and some X-ray absorption parameters like chemical shift. The chemical shift is on the higher energy side of the metal edge in these complexes. The result obtained in these studies shows that the topological indices of organic molecule acting as a legands can be used for estimating edge shift theoretically.

Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra.

PubMed

Lu, Heng; Zhang, Xuejuan; Li, Cuihong; Wei, Hedi; Liu, Qian; Li, Weiwei; Bo, Zhishan

2015-07-01

Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short-circuit current density and open-circuit voltage in comparison with the corresponding HD-PDFC-DTBT (HD)- and DT-PDPPTPT (DPP)-based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thin films with disordered nanohole patterns for solar radiation absorbers

NASA Astrophysics Data System (ADS)

Fang, Xing; Lou, Minhan; Bao, Hua; Zhao, C. Y.

2015-06-01

The radiation absorption in thin films with three disordered nanohole patterns, i.e., random position, non-uniform radius, and amorphous pattern, are numerically investigated by finite-difference time-domain (FDTD) simulations. Disorder can alter the absorption spectra and has an impact on the broadband absorption performance. Compared to random position and non-uniform radius nanoholes, amorphous pattern can induce a much better integrated absorption. The power density spectra indicate that amorphous pattern nanoholes reduce the symmetry and provide more resonance modes that are desired for the broadband absorption. The application condition for amorphous pattern nanoholes shows that they are much more appropriate in absorption enhancement for weak absorption materials. Amorphous silicon thin films with disordered nanohole patterns are applied in solar radiation absorbers. Four configurations of thin films with different nanohole patterns show that interference between layers in absorbers will change the absorption performance. Therefore, it is necessary to optimize the whole radiation absorbers although single thin film with amorphous pattern nanohole has reached optimal absorption.

Quantification of Material Fluorescence and Light Scattering Cross Sections Using Ratiometric Bandwidth-Varied Polarized Resonance Synchronous Spectroscopy.

PubMed

Xu, Joanna Xiuzhu; Hu, Juan; Zhang, Dongmao

2018-05-25

Presented herein is the ratiometric bandwidth-varied polarized resonance synchronous spectroscopy (BVPRS2) method for quantification of material optical activity spectra. These include the sample light absorption and scattering cross-section spectrum, the scattering depolarization spectrum, and the fluorescence emission cross-section and depolarization spectrum in the wavelength region where the sample both absorbs and emits. This ratiometric BVPRS2 spectroscopic method is a self-contained technique capable of quantitatively decoupling material fluorescence and light scattering signal contribution to its ratiometric BVPRS2 spectra through the linear curve-fitting of the ratiometric BVPRS2 signal as a function of the wavelength bandwidth used in the PRS2 measurements. Example applications of this new spectroscopic method are demonstrated with materials that can be approximated as pure scatterers, simultaneous photon absorbers/emitters, simultaneous photon absorbers/scatterers, and finally simultaneous photon absorbers/scatterers/emitters. Because the only instruments needed for this ratiometric BVPRS2 technique are the conventional UV-vis spectrophotometer and spectrofluorometer, this work should open doors for routine decomposition of material UV-vis extinction spectrum into its absorption and scattering component spectra. The methodology and insights provided in this work should be of broad significance to all chemical research that involves photon/matter interactions.

Core x-ray spectra in semiconductors and the Mahan-Nozieres-De Dominicis model

NASA Astrophysics Data System (ADS)

Livins, Peteris

1998-10-01

The Mahan-Nozières-De Dominicis (MND) model of core x-ray spectra is examined for semiconductors. Due to the finite band gap, the Anderson orthogonality does not occur, and thus spectra near the band edge can be calculated without the shakeup contribution. For semiconductors, and not only for metals, we investigate whether the remaining many-particle dynamic exchange effect of the MND model, or so-called replacement, can significantly alter x-ray spectral shapes near the band edge from those obtained from a straightforward final-state rule. For both emission and absorption, in the absence of shakeup, an exact formulation suitable for materials with band structure is discussed. A numerical model for a semiconductor with a 1-eV band gap demonstrates the band-edge modifications, and shows a 50% effect at the band edge, indicating that this dynamic exchange effect can be significant and should be considered in any specific emission or absorption calculation for a semiconductor. Although the ineffectiveness of the orthogonality theorem in semiconductors is emphasized, a suppression near the band edge also remains a possibility. Included is a discussion on the breakdown of the final-state rule. In addition, connection is made to the determinantal approach of Ohtaka and Tanabe.

Characterization of emission properties of Er3+ ions in TeO2-CdF2-WO3 glasses.

PubMed

Bilir, G; Mustafaoglu, N; Ozen, G; DiBartolo, B

2011-12-01

TeO(2)-CdF(2)-WO(3) glasses with various compositions and Er(3+) concentrations were prepared by conventional melting method. Their optical properties were studied by measuring the absorption, luminescence spectra and the decay patterns at room temperature. From the optical absorption spectra the Judd-Ofelt parameters (Ω(t)), transition probabilities, branching ratios of various transitions, and radiative lifetimes were calculated. The absorption and emission cross-section spectra of the (4)I(15/2) to (4)I(13/2) transition of erbium were determined. Emission quantum efficiencies and the average critical distance R(0) which provides a measure for the strength of cross relaxation were determined. Copyright © 2011 Elsevier B.V. All rights reserved.

Comparison of experimental and calculated chiroptical spectra for chiral molecular structure determination.

PubMed

Polavarapu, Prasad L; Covington, Cody L

2014-09-01

For three different chiroptical spectroscopic methods, namely, vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and Raman optical activity (ROA), the measures of similarity of the experimental spectra to the corresponding spectra predicted using quantum chemical theories are summarized. In determining the absolute configuration and/or predominant conformations of chiral molecules, these similarity measures provide numerical estimates of agreement between experimental observations and theoretical predictions. Selected applications illustrating the similarity measures for absorption, circular dichroism, and corresponding dissymmetry factor (DF) spectra, in the case of VCD and ECD, and for Raman, ROA, and circular intensity differential (CID) spectra in the case of ROA, are presented. The analysis of similarity in DF or CID spectra is considered to be much more discerning and accurate than that in absorption (or Raman) and circular dichroism (or ROA) spectra, undertaken individually. © 2014 Wiley Periodicals, Inc.

Electrochemical and PM-IRRAS Studies of the Effect of Cholesterol on the Structure of a DMPC Bilayer Supported at an Au (111) Electrode Surface, Part 1: Properties of the Acyl Chains

PubMed Central

Bin, Xiaomin; Horswell, Sarah L.; Lipkowski, Jacek

2005-01-01

Charge density measurements and polarization modulation infrared reflection absorption spectroscopy were employed to investigate the spreading of small unilamellar vesicles of a dimyristoylphosphatidylcholine (DMPC)/cholesterol (7:3 molar ratio) mixture onto an Au (111) electrode surface. The electrochemical experiments demonstrated that vesicles fuse and spread onto the Au (111) electrode surface, forming a bilayer, at rational potentials −0.4 V < (E − Epzc) < 0.4 V or field strength <6×107 V m−1. Polarization modulation infrared reflection absorption spectroscopy experiments provided information concerning the conformation and orientation of the acyl chains of DMPC molecules. Deuterated DMPC was used to subtract the contribution of C-H stretching bands of cholesterol and of the polar head region of DMPC from spectra in the C-H stretching region. The absorption spectra of the C-H stretch bands in the acyl chains were determined in this way. The properties of the DMPC/cholesterol bilayer have been compared with the properties of a pure DMPC bilayer. The presence of 30% cholesterol gives a thicker and more fluid bilayer characterized by a lower capacity and lower tilt angle of the acyl chains. PMID:15849259

Light absorption coefficients by phytoplankton pigments, suspended particles and colored dissolved organic matter in the Crimea coastal water (the Black sea) in June 2016

NASA Astrophysics Data System (ADS)

Moiseeva, N.; Churilova, T.; Efimova, T.; Krivenko, O.; Latushkin, A.

2017-11-01

Variability of the bio-optical properties of the Crimean coastal waters in June 2016 has been analyzed. The type of vertical distribution chlorophyll a concentration and phytoplankton light absorption coefficients and spectra shape differed between shallow and deeper water. In the deeper water seasonal stratification divided euphotic zone into layers with different environmental conditions. In the deeper part of the euphotic zone (below the thermocline) phytoplankton absorption spectra had local maximum at 550 nm, which was likely to be associated with high abundance of cyanobacteria (Synechococcus sps.) in the phytoplankton community. The concentration of chlorophyll a specific light absorption coefficient of phytoplankton decreased with depth (especially pronounced in the blue domain of the spectrum). In the shallow water the vertical distributions of all absorption properties were relatively homogeneous due to vertical water mixing. In the shallow water non-algal particles light absorption coefficient and its contribution to total particulate absorption were higher than those in the deeper water. The non-algal particles (NAP) and colored dissolved organic matter (CDOM) light absorption spectra were well described by an exponential function with a slope averaging 0.010 nm-1 (SD = 0.001 nm-1) and 0.022 nm-1 (SD = 0.0060 nm-1), correspondingly. The CDOM absorption at 440 nm and slope coefficient varied significantly across the investigated area, which was possibly associated with the terrestrial influences. The assessment of the contribution of phytoplankton, NAP and CDOM to total light absorption showed that CDOM dominated in the absorption at 440 nm.

Discrimination of Medicine Radix Astragali from Different Geographic Origins Using Multiple Spectroscopies Combined with Data Fusion Methods

NASA Astrophysics Data System (ADS)

Wang, Hai-Yan; Song, Chao; Sha, Min; Liu, Jun; Li, Li-Ping; Zhang, Zheng-Yong

2018-05-01

Raman spectra and ultraviolet-visible absorption spectra of four different geographic origins of Radix Astragali were collected. These data were analyzed using kernel principal component analysis combined with sparse representation classification. The results showed that the recognition rate reached 70.44% using Raman spectra for data input and 90.34% using ultraviolet-visible absorption spectra for data input. A new fusion method based on Raman combined with ultraviolet-visible data was investigated and the recognition rate was increased to 96.43%. The experimental results suggested that the proposed data fusion method effectively improved the utilization rate of the original data.

Non-destructive inspections of illicit drugs in envelope using terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Li, Ning; Shen, Jingling; Lu, Meihong; Jia, Yan; Sun, Jinhai; Liang, Laishun; Shi, Yanning; Xu, Xiaoyu; Zhang, Cunlin

2006-09-01

The absorption spectra of two illicit drugs, methylenedioxyamphetarnine (MDA) and methamphetamine (MA), within and without two conventional envelopes are studied using terahertz time-domain spectroscopy technique. The characteristic absorption spectra of MDA and MA are obtained in the range of 0.2 THz to 2.5 THz. MDA has an obvious absorption peak at 1.41 THz while MA has obvious absorption peaks at 1.23 THz, 1.67 THz, 1.84 THz and 2.43 THz. We find that the absorption peaks of MDA and MA within the envelopes are almost the same as those without the envelopes respectively although the two envelopes have some different absorption in THz waveband. This result indicates that the type of illicit drugs in envelopes can be determined by identifying their characteristic absorption peaks, and THz time-domain spectroscopy is one of the most powerful candidates for illicit drugs inspection.

Decomposition of mineral absorption bands using nonlinear least squares curve fitting: Application to Martian meteorites and CRISM data

NASA Astrophysics Data System (ADS)

Parente, Mario; Makarewicz, Heather D.; Bishop, Janice L.

2011-04-01

This study advances curve-fitting modeling of absorption bands of reflectance spectra and applies this new model to spectra of Martian meteorites ALH 84001 and EETA 79001 and data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). This study also details a recently introduced automated parameter initialization technique. We assess the performance of this automated procedure by comparing it to the currently available initialization method and perform a sensitivity analysis of the fit results to variation in initial guesses. We explore the issues related to the removal of the continuum, offer guidelines for continuum removal when modeling the absorptions and explore different continuum-removal techniques. We further evaluate the suitability of curve fitting techniques using Gaussians/Modified Gaussians to decompose spectra into individual end-member bands. We show that nonlinear least squares techniques such as the Levenberg-Marquardt algorithm achieve comparable results to the MGM model ( Sunshine and Pieters, 1993; Sunshine et al., 1990) for meteorite spectra. Finally we use Gaussian modeling to fit CRISM spectra of pyroxene and olivine-rich terrains on Mars. Analysis of CRISM spectra of two regions show that the pyroxene-dominated rock spectra measured at Juventae Chasma were modeled well with low Ca pyroxene, while the pyroxene-rich spectra acquired at Libya Montes required both low-Ca and high-Ca pyroxene for a good fit.

Optical spectroscopy of interplanetary dust collected in the earth's stratosphere

NASA Technical Reports Server (NTRS)

Fraundorf, P.; Patel, R. I.; Shirck, J.; Walker, R. M.; Freeman, J. J.

1980-01-01

Optical absorption spectra of interplanetary dust particles 2-30 microns in size collected in the atmosphere at an altitude of 20 km by inertial impactors mounted on NASA U-2 aircraft are reported. Fourier transform absorption spectroscopy of crushed samples of the particles reveals a broad feature in the region 1300-800 kaysers which has also been found in meteorite and cometary dust spectra, and a weak iron crystal field absorption band at approximately 9800 kaysers, as is observed in meteorites. Work is currently in progress to separate the various components of the interplanetary dust particles in order to evaluate separately their contributions to the absorption.

One- and two-photon absorption spectra of the yellow fluorescent protein citrine: effects of intramolecular electron-vibrational coupling and intermolecular interactions

NASA Astrophysics Data System (ADS)

Chen, Fasheng; Zhao, Xinyi; Liang, WanZhen

2018-04-01

Both the vibrationally resolved and statistically averaged one-photon absorption (OPA) and two-photon absorption (TPA) spectra of the anionic form of chromophore (AC) in its micro-environment of yellow fluorescent protein (YFP) Citrine have been calculated. The result comparison has been made with those of the AC model compounds in vacuo and methanol solution, which allows us to allocate the individual contribution of the intramolecular electron-vibrational coupling, the electrostatic π-stacking interaction between Tyr203 and AC, and the interaction between AC and its micro-environment to the spectra. The results reveal that the non-Condon vibronic coupling effect is responsible for the blue shift of TPA absorption maximum compared with its OPA counterpart corresponding to S0 → S1, and that the π-stacking interaction between Tyr203 and AC alters the relative intensities of TPA maxima, which further enhances the higher-energy vibronic peaks and weakens the lowest-energy peak. The statically averaged OPA and TPA spectra calculated by quantum mechanics/molecular mechanics (QM/MM) methods based on Born-Oppenheimer molecular dynamics simulation largely deviate the experimental spectral lineshapes, which further verifies the significant contribution of non-Condon vibronic coupling effect on the spectra. The interaction of individual amino acid residue or water close to AC+Tyr203 has different effects on the spectra, which may increase/decrease the excitation energy depending on its position and electronic property.

Solvatochromic Effects on the Absorption Spectrum of 2-Thiocytosine

PubMed Central

2017-01-01

The solvatochromic effects of six different solvents on the UV absorption spectrum of 2-thiocytosine have been studied by a combination of experimental and theoretical techniques. The steady-state absorption spectra show significant shifts of the absorption bands, where in more polar solvents the first absorption maximum shifts to higher transition energies and the second maximum to lower energies. The observed solvatochromic shifts have been rationalized using three popular solvatochromic scales and with high-level multireference quantum chemistry calculations including implicit and explicit solvent effects. It has been found that the dipole moments of the excited states account for some general shifts in the excitation energies, whereas the explicit solvent interactions explain the differences in the spectra recorded in the different solvents. PMID:28452483

Absorption of Dy3+ and Nd3+ ions in Ba R 2F8 single crystals

NASA Astrophysics Data System (ADS)

Apollonov, V. V.; Pushkar', A. A.; Uvarova, T. V.; Chernov, S. P.

2008-09-01

The Dy3+ absorption and excitation spectra of BaY2F8 and BaYb2F8 single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4 f-5 d transitions in the range (56-78) × 10-3 cm-1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50-56) × 10-3 cm-1. The Nd3+ absorption spectra of BaY2F8 single crystals are studied in the range (34-82) × 10-3 cm-1 at 300 K for different crystal orientations.

Ultraviolet absorption spectra of shock-heated carbon dioxide and water between 900 and 3050 K

NASA Astrophysics Data System (ADS)

Schulz, C.; Koch, J. D.; Davidson, D. F.; Jeffries, J. B.; Hanson, R. K.

2002-03-01

Spectrally resolved UV absorption cross-sections between 190 and 320 nm were measured in shock-heated CO 2 between 880 and 3050 K and H 2O between 1230 and 2860 K. Absorption spectra were acquired with 10 μs time resolution using a unique kinetic spectrograph, thereby enabling comparisons with time-dependent chemical kinetic modeling of post-shock thermal decomposition and chemical reactions. Although room temperature CO 2 is transparent (σ<10 -22 cm2) at wavelengths longer than 200 nm, hot CO 2 has significant absorption (σ>10 -20 cm2) extending to wavelengths longer than 300 nm. The temperature dependence of CO 2 absorption strongly suggests sharply increased transition probabilities from excited vibrational levels.

Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolshov, Mikhail A; Kuritsyn, Yu A; Liger, V V

2009-09-30

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 {mu}m. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature andmore » H{sub 2}O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged ({approx}50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is {approx}40 K. (laser applications and other topics in quantum electronics)« less

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Bolshov, Mikhail A.; Kuritsyn, Yu A.; Liger, V. V.; Mironenko, V. R.; Leonov, S. B.; Yarantsev, D. A.

2009-09-01

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 μm. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature and H2O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged (~50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is ~40 K.

Surface Material Analysis of the S-type Asteroids: Removing the Space Weathering Effect from Reflectance Spectrum

NASA Technical Reports Server (NTRS)

Ueda, Y.; Miyamoto, M.; Mikouchi, T.; Hiroi, T.

2003-01-01

Recent years, many researchers have been observing a lot of asteroid reflectance spectra in the UV, visible to NIR at wavelength region. Reflectance spectroscopy of asteroid at this range should bring us a lot of information about its surface materials. Pyroxene and olivine have characteristic absorption bands in this wavelength range. Low-Ca pyroxene has two absorption bands around 0.9 microns and 1.9 microns. The more Ca and Fe content, the longer both absorption band centers. On the other hand, reflectance spectrum of olivine has three complicated absorption bands around 1 m, and no absorption feature around 2 microns. In general, reflectance spectra of many asteroids that are considered to be silicate rich (i.e., S- and A type asteroids) show redder slope and more subdued absorption bands than those of terrestrial minerals and meteorites. These features are now believed to be caused by the space weathering effect, which is probably caused by micrometeorite bombardment and/or solar wind. This process causes nanophase reduced iron (npFe(sup 0)) particles near the surface of mineral grains, which leads the optical change. Therefore, the space weathering effect should be removed from asteroid reflectance spectra to compare with those of meteorite and terrestrial minerals. In this report, we will apply the expanded modified Gaussian model (MGM) to the reflectance spectra of S-type asteroids 7 Iris and 532 Herculina and compare them with those of meteorites.

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 absorbance...

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 absorbance...

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 absorbance...

The Transiting Exocomets in the HD 172555 System

NASA Technical Reports Server (NTRS)

Grady, C. A.; Brown, A.; Kamp, I.; Roberge, A.; Riviere-Marichalar, P.; Welsh, B.

2017-01-01

The Earth is thought to have formed dry, in a part of the Solar Nebula deficient in organic material, and to have acquired its organics and water through bombardment by minor bodies. Observations of this process in well-dated systems can provide insight into the probable origin and composition of the bombarding parent bodies. Transiting cometary activity has previously been reported in Ca II for the late-A member of the 241 Myr old Pictoris Moving Group member, HD 172555(Kiefer et al. 2014). We present HST STIS and COS spectra of HD 172555 demonstrating that the star has chromospheric emission and variable in falling gas features in transitions of silicon and carbon ions at times when no Fe II absorption is seen in the UV data, and no Ca II absorption is seen in contemporary optical spectra. The lack of CO absorption and stable gas absorption at the system velocity is consistent with the absence of a cold Kuiper belt analog (Riviere-Marichalar et al. 2012) in this system. The presence of infall in some species at one epoch and others at different epochs suggests that, like Pictoris, there may be more than one family of exocomets. If perturbed into star-grazing orbits by the same mechanism as for Pic, these data suggest that the wide planet frequency among A-early F stars in the PMG is at least 37.5, well above the frequency estimated for young moving groups independent of host star spectral type.

Moderate-resolution spectral standards from lambda 5600 to lambda 9000

NASA Technical Reports Server (NTRS)

Allen, Lori E.; Strom, Karen M.

1995-01-01

We present a grid of stellar classification spectra of moderate resolution (R approximately 1500) in the range lambda lambda 5600-9000 A, compiled from high signal-to noise spectra of 275 stars, most in the open clusters Praesepe and M67. The grid covers dwarfs from types B8 through M5, giants from G8 through M7, and subgiants from F5 through K0. We catalog atomic and molecular absorption features useful for stellar classification, and demonstrate the use of luminosity-sensitive features to distinguish between late-type dwarf and giant stars. The entire database is made available in digital format on anonymous ftp and through the World Wide Web.

Long - High Resolution Spectrum of Methane. Towards Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Daumont, Ludovic; Tyuterev, Vladimir; Regalia, Laurence; Thomas, Xavier; von der Heyden, Pierre; Nikitin, Rei; Brown, Linda

2011-06-01

The precise knowledge of the methane absorption in the study of planetary systems, and especially of Titan (Saturn's largest satellite whose atmosphere is mainly composed of nitrogen and methane at temperatures ranging between 70 K and 200 K), is of great importance because it gives access to the determination of the physical properties of these objects. The full interpretation of the Titan data returned by the ground-based and space observations has been hindered by the lack of precise knowledge of the methane absorption which dominates Titan's near infrared spectra. We investigate the methane spectra in the closest conditions to existing Titan's spectra. We used the 50 m long cell from Reims university in front of the Home-made Fourier Transform Spectrometer to study the 12CH_4 spectra with 1603 m absorption path length, 1, 7 and 34 hPa pressures and at room temperature. The spectra was recorded in the all range from 3800 to 8100 Cm-1. The up-to-date measurements and assignments- mainly in the so called methane transparancy windows- will be presented and discussed.

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

PubMed

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

2011-06-01

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

Low-refractive-index dye-aggregate films with small absorption based on anomalous dispersion.

PubMed

Wakamatsu, Takashi; Watanabe, Keita; Saito, Kazuhiro

2005-02-20

Complex-refractive-index spectra of Squarylium (SQ) dye-aggregate films deposited upon metal films have been investigated by measurements of properties of the films including absorption spectra (AS) and attenuated total reflection. Complex refractive indices are estimated by Kramers-Kronig analysis for the AS and by a theoretical curve-fitting analysis for attenuated total reflection. The dye-aggregate films exhibited an absorption that was blueshifted from that of a monomer, as a result of the H-aggregate formation of SQ molecules, and had a changing refractive index with anomalous dispersion about the H-absorption band. From both measurements of the SQ films it was found that there is a region of low absorption in the short-wavelength side of the absorption band and that the refractive index there is lower than that of glass.

Low-refractive-index dye-aggregate films with small absorption based on anomalous dispersion

NASA Astrophysics Data System (ADS)

Wakamatsu, Takashi; Watanabe, Keita; Saito, Kazuhiro

2005-02-01

Complex-refractive-index spectra of Squarylium (SQ) dye-aggregate films deposited upon metal films have been investigated by measurements of properties of the films including absorption spectra (AS) and attenuated total reflection. Complex refractive indices are estimated by Kramers-Kronig analysis for the AS and by a theoretical curve-fitting analysis for attenuated total reflection. The dye-aggregate films exhibited an absorption that was blueshifted from that of a monomer, as a result of the H-aggregate formation of SQ molecules, and had a changing refractive index with anomalous dispersion about the H-absorption band. From both measurements of the SQ films it was found that there is a region of low absorption in the short-wavelength side of the absorption band and that the refractive index there is lower than that of glass.

A Hubble Space Telescope Survey of Intrinsic Absorption in Nearby AGN

NASA Astrophysics Data System (ADS)

Dashtamirova, Dzhuliya; Dunn, Jay P.; Crenshaw, D. Michael

2017-01-01

We present a survey of the intrinsic UV absorption lines in active galactic nuclei (AGN). We limit our study to the ultraviolet spectra of type 1 AGN with a redshift of z < 0.15 as a continuation of the Dunn et al. (2007, 2008) and Crenshaw et al. (1999) studies of smaller samples. We identify approximately 90 AGN fit our redshift specifications in the Mikulski Archive for Space Telescopes (MAST) database with Cosmic Origin Spectrograph (COS) observations. We download and co-add all of the COS spectra. We find that about 80 of these are type 1 AGN. We normalize the COS spectra and identify all of the intrinsic Lyman-alpha, N V, Si IV, and C IV intrinsic absorption features. From these data, we determine the fraction of type 1 AGN with intrinsic absorption in this redshift range and find the global covering factors of the absorbers. We also identify low ionization species as well as excited state lines. A number of objects have multiple epoch COS and/or Space Telescope Imaging Spectrograph (STIS) observations, which we use to investigate the absorption variability.

Absorption and resonance Raman characteristics of β-carotene in water-ethanol mixtures, emulsion and hydrogel

NASA Astrophysics Data System (ADS)

Meinhardt-Wollweber, Merve; Suhr, Christian; Kniggendorf, Ann-Kathrin; Roth, Bernhard

2018-05-01

Absorption or resonance Raman scattering are often used to identify and even quantify carotenoids in situ. We studied the absorption spectra, the Raman spectra and their resonance behavior of β-carotene in different molecular environments set up as mixtures from lipid (emulsion) and non-polar (ethanol) solvents and a polar component (water) with regard to their application as references for in situ measurement. We show how both absorption profiles and resonance spectra of β-carotene strongly depend on the molecular environment. Most notably, our data suggests that the characteristic bathochromic absorption peak of J-aggregates does not contribute to carotenoid resonance conditions, and show how the Raman shift of the C=C stretching mode is dependent on both, the molecular environment and the excitation wavelength. Overall, the spectroscopic data collected here is highly relevant for the interpretation of in situ spectroscopic data in terms of carotenoid identification and quantification by resonance Raman spectroscopy as well as the preparation of reference samples. In particular, our data promotes careful consideration of appropriate molecular environment for reference samples.

Numerical indicators of absorption spectra of green leaf extract obtained from plants of different life forms.

PubMed

Koldaev, Vladimir M; Manyakhin, Artem Yu

2018-06-05

The study was carried out using 58 species of terrestrial plants of different life forms at the start of their fruiting stage. Photoreceptive systems of the leaves were assessed by means of unconventional numerical indicators of absorption spectra, relative photoabsorption coefficient, photosynthetic pigments' integral absorption intensity and relative absorption intensity coefficient. As the study showed, the leaves of all trees and light-demanding grasses favoring open spaces, which were subjected to the study were featured by the lowest values of numerical indicators of absorption spectra (NIAS). Shade-demanding grasses, which grow beneath the canopy, by contrast, were featured by the highest NIAS values. These values of the shrub leaves were in between those of light-demanding plants and shade-demanding ones. The results obtained are consistent with modern visions concerning the biochemistry and the physiology of plants' photoreceptive system. It is appropriate to apply the NIAS, which were used in this study and reflect a leaf's photoreceptive properties, as spectrophotometric criteria for monitoring and environmental management of natural plant resources and agricultural plants. Copyright © 2018 Elsevier B.V. All rights reserved.

Evanescent-wave comb spectroscopy of liquids with strongly dispersive optical fiber cavities

NASA Astrophysics Data System (ADS)

Avino, S.; Giorgini, A.; Salza, M.; Fabian, M.; Gagliardi, G.; De Natale, P.

2013-05-01

We demonstrate evanescent-wave fiber cavity-enhanced spectroscopy in the liquid phase using a near-infrared frequency comb. Exploiting strong fiber-dispersion effects, we show that liquid absorption spectra can be recorded without any external dispersive element. The fiber cavity is used both as sensor and spectrometer. The resonance modes are frequency locked to the comb teeth while the cavity photon lifetime is measured over 155 nm, from 1515 nm to 1670 nm, where absorption bands of liquid polyamines are detected as a proof of concept. Our fiber spectrometer lends itself to in situ, real-time chemical analysis in environmental monitoring, biomedical assays, and micro-opto-fluidic systems.

Stimulated emission and lasing from all-inorganic perovskite quantum dots

NASA Astrophysics Data System (ADS)

Sun, Handong; Wang, Yue; Li, Xiaoming; Haibo, Zeng

We present superior optical gain and lasing properties in a new class of emerging quantum materials, the colloidal all-inorganic cesium lead halide perovskite quantum dots (IPQDs) (CsPbX3, X = Cl, Br, I). Our result has indicated that such material system show combined merits of both colloidal quantum dots and halide perovskites. Low-threshold and ultrastable stimulated emission was demonstrated under atmospheric condition. The flexibility and advantageous optical gain properties of these CsPbX3 IPQDs were manifested by demonstration of an optically pumped micro-laser. The nonlinear optical properties including the multi-photon absorption and resultant photoluminescence of the CsPbX3 nanocrystals were investigated. A large two-photon absorption cross-section of up to ~1.2×105 GM is determined from 9 nm-sized CsPbBr3 nanocrystals. Moreover, low-threshold frequency-upconverted stimulated emission by two-photon absorption was observed from the thin films of close-packed CsPbBr3 nanocrystals. We further realize the three-photon pumped stimulated emission in green spectra range from colloidal IPQD.

Frenkel-exciton decomposition analysis of circular dichroism and circularly polarized luminescence for multichromophoric systems.

PubMed

Shiraogawa, Takafumi; Ehara, Masahiro; Jurinovich, Sandro; Cupellini, Lorenzo; Mennucci, Benedetta

2018-06-15

Recently, a method to calculate the absorption and circular dichroism (CD) spectra based on the exciton coupling has been developed. In this work, the method was utilized for the decomposition of the CD and circularly polarized luminescence (CPL) spectra of a multichromophoric system into chromophore contributions for recently developed through-space conjugated oligomers. The method which has been implemented using rotatory strength in the velocity form and therefore it is gauge-invariant, enables us to evaluate the contribution from each chromophoric unit and locally excited state to the CD and CPL spectra of the total system. The excitonic calculations suitably reproduce the full calculations of the system, as well as the experimental results. We demonstrate that the interactions between electric transition dipole moments of adjacent chromophoric units are crucial in the CD and CPL spectra of the multichromophoric systems, while the interactions between electric and magnetic transition dipole moments are not negligible. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Leaf absorbance and photosynthesis

NASA Technical Reports Server (NTRS)

Schurer, Kees

1994-01-01

The absorption spectrum of a leaf is often thought to contain some clues to the photosynthetic action spectrum of chlorophyll. Of course, absorption of photons is needed for photosynthesis, but the reverse, photosynthesis when there is absorption, is not necessarily true. As a check on the existence of absorption limits we measured spectra for a few different leaves. Two techniques for measuring absorption have been used, viz. the separate determination of the diffuse reflectance and the diffuse transmittance with the leaf at a port of an integrating sphere and the direct determination of the non-absorbed fraction with the leaf in the sphere. In a cross-check both methods yielded the same results for the absorption spectrum. The spectrum of a Fuchsia leaf, covering the short-wave region from 350 to 2500 nm, shows a high absorption in UV, blue and red, the well known dip in the green and a steep fall-off at 700 nm. Absorption drops to virtually zero in the near infrared, with subsequent absorptions, corresponding to the water absorption bands. In more detailed spectra, taken at 5 nm intervals with a 5 nm bandwidth, differences in chlorophyll content show in the different depths of the dip around 550 nm and in a small shift of the absorption edge at 700 nm. Spectra for Geranium (Pelargonium zonale) and Hibiscus (with a higher chlorophyll content) show that the upper limit for photosynthesis can not be much above 700 nm. No evidence, however, is to be seen of a lower limit for photosynthesis and, in fact, some experiments down to 300 nm still did not show a decrease of the absorption although it is well recognized that no photosynthesis results with 300 nm wavelengths.

Molecfit: A general tool for telluric absorption correction. II. Quantitative evaluation on ESO-VLT/X-Shooterspectra

NASA Astrophysics Data System (ADS)

Kausch, W.; Noll, S.; Smette, A.; Kimeswenger, S.; Barden, M.; Szyszka, C.; Jones, A. M.; Sana, H.; Horst, H.; Kerber, F.

2015-04-01

Context. Absorption by molecules in the Earth's atmosphere strongly affects ground-based astronomical observations. The resulting absorption line strength and shape depend on the highly variable physical state of the atmosphere, i.e. pressure, temperature, and mixing ratio of the different molecules involved. Usually, supplementary observations of so-called telluric standard stars (TSS) are needed to correct for this effect, which is expensive in terms of telescope time. We have developed the software package molecfit to provide synthetic transmission spectra based on parameters obtained by fitting narrow ranges of the observed spectra of scientific objects. These spectra are calculated by means of the radiative transfer code LBLRTM and an atmospheric model. In this way, the telluric absorption correction for suitable objects can be performed without any additional calibration observations of TSS. Aims: We evaluate the quality of the telluric absorption correction using molecfit with a set of archival ESO-VLT/X-Shooter visible and near-infrared spectra. Methods: Thanks to the wavelength coverage from the U to the K band, X-Shooter is well suited to investigate the quality of the telluric absorption correction with respect to the observing conditions, the instrumental set-up, input parameters of the code, the signal-to-noise of the input spectrum, and the atmospheric profiles. These investigations are based on two figures of merit, Ioff and Ires, that describe the systematic offsets and the remaining small-scale residuals of the corrections. We also compare the quality of the telluric absorption correction achieved with molecfit to the classical method based on a telluric standard star. Results: The evaluation of the telluric correction with molecfit shows a convincing removal of atmospheric absorption features. The comparison with the classical method reveals that molecfit performs better because it is not prone to the bad continuum reconstruction, noise, and intrinsic spectral features introduced by the telluric standard star. Conclusions: Fitted synthetic transmission spectra are an excellent alternative to the correction based on telluric standard stars. Moreover, molecfit offers wide flexibility for adaption to various instruments and observing sites. http://www.eso.org/sci/software/pipelines/skytools/

Random-hole optical fiber evanescent-wave gas sensing.

PubMed

Pickrell, G; Peng, W; Wang, A

2004-07-01

Research on development of optical gas sensors based on evanescent-wave absorption in random-hole optical fibers is described. A process to produce random-hole optical fibers was recently developed that uses a novel in situ bubble formation technique. Gas molecules that exhibit characteristic vibrational absorption lines in the near-IR region that correspond to the transmission window for silica optical fiber have been detected through the evanescent field of the guided mode in the pore region. The presence of the gas molecules in the holes of the fiber appears as a loss at wavelengths that are characteristic of the particular gas species present in the holes. An experimental setup was constructed with these holey fibers for detection of acetylene gas. The results clearly demonstrate the characteristic absorptions in the optical spectra that correspond to the narrow-line absorptions of the acetylene gas, and this represents what is to our knowledge the first report of random-hole fiber gas sensing in the literature.

Terahertz spectroscopic investigation of Chinese herbal medicine

NASA Astrophysics Data System (ADS)

Xiao-li, Zhao; Jiu-sheng, Li

2011-02-01

The absorption spectra of panax notoginseng and glycyrrhiza in the frequency range of 0.2~1.6THz has been measured with terahertz time-domin spectroscopy at room temperature. Simultaneously, the corresponding theoretical spectra were given by using density functional theory methods. It was found that the absorption peaks of the two molecules obtained by theoretical were in good agreement with the experimental results.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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

PubMed

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

2011-05-12

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

Effect of X-ray irradiation on the optical absorption of СdSe1-xTex nanocrystals embedded in borosilicate glass

NASA Astrophysics Data System (ADS)

Prymak, M. V.; Azhniuk, Yu. M.; Solomon, A. M.; Krasilinets, V. M.; Lopushansky, V. V.; Bodnar, I. V.; Gomonnai, A. V.; Zahn, D. R. T.

2012-07-01

The effect of X-ray irradiation on the optical absorption spectra of CdSe1-xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature.

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.

Modulation of intersubband light absorption and interband photoluminescence in double GaAs/AlGaAs quantum wells under strong lateral electric fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balagula, R. M., E-mail: rmbal@spbstu.ru; Vinnichenko, M. Ya., E-mail: mvin@spbstu.ru; Makhov, I. S.

The effect of a lateral electric field on the mid-infrared absorption and interband photoluminescence spectra in double tunnel-coupled GaAs/AlGaAs quantum wells is studied. The results obtained are explained by the redistribution of hot electrons between quantum wells and changes in the space charge in the structure. The hot carrier temperature is determined by analyzing the intersubband light absorption and interband photoluminescence modulation spectra under strong lateral electric fields.

Optimal extraction of quasar Lyman limit absorption systems from the IUE archive

NASA Technical Reports Server (NTRS)

Tytler, David

1992-01-01

The IUE archive contains a wealth of information on Lyman limit absorption systems (LLS) in quasar spectra. QSO spectra from the IUE data base were optimally extracted, coadded, and analyzed to yield a homogeneous samples of LLS at low red shifts. This sample comprise 36 LLS, twice the number previously analyzed low z samples. These systems are ideal for the determination of the origin, redshift evolution, ionization, velocity dispersions and the metal abundances of absorption systems. Two of them are also excellent targets for the primordial Deuterium to Hydrogen ratio.

Tuning the electrical and optical anisotropy of a monolayer black phosphorus magnetic superlattice

NASA Astrophysics Data System (ADS)

Li, X. J.; Yu, J. H.; Luo, K.; Wu, Z. H.; Yang, W.

2018-04-01

We investigate theoretically the effects of modulated periodic perpendicular magnetic fields on the electronic states and optical absorption spectrum in monolayer black phosphorus (phosphorene). We demonstrate that different phosphorene magnetic superlattice (PMS) orientations can give rise to distinct energy spectra, i.e. tuning the intrinsic electronic anisotropy. Rashba spin-orbit coupling (RSOC) develops a spin-splitting energy dispersion in this phosphorene magnetic superlattice. Anisotropic momentum-dependent carrier distributions along/perpendicular to the magnetic strips are demonstrated. The manipulations of these exotic electronic properties by tuning superlattice geometry, magnetic field and the RSOC term are addressed systematically. Accordingly, we find bright-to-dark transitions in the ground-state electron-hole pair transition rate spectrum and the PMS orientation-dependent anisotropic optical absorption spectrum. This feature offers us a practical way of modulating the electronic anisotropy in phosphorene by magnetic superlattice configurations and detecting this modulation capability by using an optical technique.

Multispecies absorption spectroscopy of detonation events at 100  kHz using a fiber-coupled, time-division-multiplexed quantum-cascade-laser system.

PubMed

Rein, Keith D; Roy, Sukesh; Sanders, Scott T; Caswell, Andrew W; Schauer, Frederick R; Gord, James R

2016-08-10

A mid-infrared fiber-coupled laser system constructed around three time-division-multiplexed quantum-cascade lasers capable of measuring the absorption spectra of CO, CO₂, and N₂O at 100 kHz over a wide range of operating pressures and temperatures is demonstrated. This system is first demonstrated in a laboratory burner and then used to measure temperature, pressure, and concentrations of CO, CO₂, and N₂O as a function of time in a detonated mixture of N₂O and C₃H₈. Both fuel-rich and fuel-lean detonation cases are outlined. High-temperature fluctuations during the blowdown are observed. Concentrations of CO are shown to decrease with time for fuel-lean conditions and increase for fuel-rich conditions.

Real-time trace gas sensor using a multimode diode laser and multiple-line integrated cavity enhanced absorption spectroscopy.

PubMed

Karpf, Andreas; Rao, Gottipaty N

2015-07-01

We describe and demonstrate a highly sensitive trace gas sensor based on a simplified design that is capable of measuring sub-ppb concentrations of NO2 in tens of milliseconds. The sensor makes use of a relatively inexpensive Fabry-Perot diode laser to conduct off-axis cavity enhanced spectroscopy. The broad frequency range of a multimode Fabry-Perot diode laser spans a large number of absorption lines, thereby removing the need for a single-frequency tunable laser source. The use of cavity enhanced absorption spectroscopy enhances the sensitivity of the sensor by providing a pathlength on the order of 1 km in a small volume. Off-axis alignment excites a large number of cavity modes simultaneously, thereby reducing the sensor's susceptibility to vibration. Multiple-line integrated absorption spectroscopy (where one integrates the absorption spectra over a large number of rovibronic transitions of the molecular species) further improves the sensitivity of detection. Relatively high laser power (∼400  mW) is used to compensate for the low coupling efficiency of a broad linewidth laser to the optical cavity. The approach was demonstrated using a 407 nm diode laser to detect trace quantities of NO2 in zero air. Sensitivities of 750 ppt, 110 ppt, and 65 ppt were achieved using integration times of 50 ms, 5 s, and 20 s respectively.

Visible Spectroscopic Observation Of Asteroid 162173 (1999ju3) With The Gemini-s Telescope

NASA Astrophysics Data System (ADS)

Sugita, Seiji; Kuroda, D.; Kameda, S.; Hasegawa, S.; Kamata, S.; Abe, M.; Ishiguro, M.; Takato, N.; Yoshikawa, M.

2012-10-01

Asteroid 162173 (1999JU3; hereafter JU3) is the target of the Hayabusa-2 mission. Its visible reflectance spectra have been observed a few times [1,2], and obtained spectra exhibit a wide variety of spectral patterns ranging from a spectra with absorption in the UV region (May 1999) to a flat spectrum with a faint broad absorption centered around 0.6 microns (September 2007) and that with UV absorption and strong broad absorption centered around 0.7 micron (July 2007). The apparent large spectral variation may be due to variegation on the asteroid surface. Such variegation would make a large influence on remote sensing strategy for Hayabusa-2 before its sampling operations. In order to better constraint the spectral properties of JU3, we conducted visible spectroscopic observations at the GEMINI-South observatory 8.1-m telescope with the GMOS instrument. We could obtain three different sets of data in June and July 2012. Although the JU3 rotation phases of two of the observation are close to each other, the other is about 120 degrees away from the two. Our preliminary analyses indicate that these three spectra are slightly reddish but generally flat across the observed wavelength range (0.47 - 0.89 microns). The observed flat spectra are most similar to the spectrum obtained in September 2007, which probably has the highest signal-to-noise ratio among the previous three spectra. This result suggests that material with a flat spectrum probably covers a dominant proportion of the JU3 surface and that the other two types of previously obtained spectra may not cover a very large fraction of the JU3 surface. [1] Binzel, R. P. et al. (2001) Icarus, 151, 139-149; [2] Vilas, F. (2008) AJ, 135, 1101-1105.

Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

PubMed

Adrowski, Michael J.; Mason, W. Roy

1997-03-26

Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

Decomposition of the fluorescence spectra of two FAD molecules in electron-transferring flavoprotein from Megasphaera elsdenii.

PubMed

Sato, Kyosuke; Nishina, Yasuzo; Shiga, Kiyoshi

2013-07-01

Electron-transferring flavoprotein (ETF) from Megasphaera elsdenii contains two FAD molecules, FAD-1 and FAD-2. FAD-2 shows an unusual absorption spectrum with a 400-nm peak. In contrast, ETFs from other sources such as pig contain one FAD and one AMP with the FAD showing a typical flavin absorption spectrum with 380- and 440-nm peaks. It is presumed that FAD-2 is the counterpart of the FAD in other ETFs. In this study, the FAD-1 and FAD-2 fluorescence spectra were determined by titration of FAD-1-bound ETF with FAD using excitation-emission matrix (EEM) fluorescence spectroscopy. The EEM data were globally analysed, and the FAD fluorescence spectra were calculated from the principal components using their respective absorption spectra. The FAD-2 fluorescence spectrum was different from that of pig ETF, which is more intense and blue-shifted. AMP-free pig ETF in acidic solution, which has a comparable absorption spectrum to FAD-2, also had a similar fluorescence spectrum. This result suggests that FAD-2 in M. elsdenii ETF and the FAD in acidic AMP-free pig ETF share a common microenvironment. A review of published ETF fluorescence spectra led to the speculation that the majority of ETF molecules in solution are in the conformation depicted by the crystal structure.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewandowski, Wojciech; Rożko, Karolina; Kijak, Jarosław

2015-07-20

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

Tunable absorption resonances in the ultraviolet for InP nanowire arrays.

PubMed

Aghaeipour, Mahtab; Anttu, Nicklas; Nylund, Gustav; Samuelson, Lars; Lehmann, Sebastian; Pistol, Mats-Erik

2014-11-17

The ability to tune the photon absorptance spectrum is an attracting way of tailoring the response of devices like photodetectors and solar cells. Here, we measure the reflectance spectra of InP substrates patterned with arrays of vertically standing InP nanowires. Using the reflectance spectra, we calculate and analyze the corresponding absorptance spectra of the nanowires. We show that we can tune absorption resonances for the nanowire arrays into the ultraviolet by decreasing the diameter of the nanowires. When we compare our measurements with electromagnetic modeling, we generally find good agreement. Interestingly, the remaining differences between modeled and measured spectra are attributed to a crystal-phase dependence in the refractive index of InP. Specifically, we find indication of significant differences in the refractive index between the modeled zinc-blende InP nanowires and the measured wurtzite InP nanowires in the ultraviolet. We believe that such crystal-phase dependent differences in the refractive index affect the possibility to excite optical resonances in the large wavelength range of 345 < λ < 390 nm. To support this claim, we investigated how resonances in nanostructures can be shifted in wavelength by geometrical tuning. We find that dispersion in the refractive index can dominate over geometrical tuning and stop the possibility for such shifting. Our results open the door for using crystal-phase engineering to optimize the absorption in InP nanowire-based solar cells and photodetectors.

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

NASA Technical Reports Server (NTRS)

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

2000-01-01

We evaluated the accuracy, sensitivity and precision of a multiple pathlength, liquid core waveguide (MPLCW) system for measuring colored dissolved organic matter (CDOM) absorption in the UV-visible spectral range (370-700 nm). The MPLCW has four optical paths (2.0, 9.8, 49.3, and 204 cm) coupled to a single Teflon AF sample cell. Water samples were obtained from inland, coastal and ocean waters ranging in salinity from 0 to 36 PSU. Reference solutions for the MPLCW were made having a refractive index of the sample. CDOM absorption coefficients, a(sub CDOM), and the slope of the log-linearized absorption spectra, S, were compared with values obtained using a dual-beam spectrophotometer. Absorption of phenol red secondary standards measured by the MPLCW at 558 nm were highly correlated with spectrophotometer values (r > 0.99) and showed a linear response across all four pathlengths. Values of a(sub CDOM) measured using the MPLCW were virtually identical to spectrophotometer values over a wide range of concentrations. The dynamic range of a(sub CDOM) for MPLCW measurements was 0.002 - 231.5/m. At low CDOM concentrations (a(sub 370) < 0.1/m) spectrophotometric a(sub CDOM) were slightly greater than MPLCW values and showed larger fluctuations at longer wavelengths due to limitations in instrument precision. In contrast, MPLCW spectra followed an exponential to 600 nm for all samples. The maximum deviation in replicate MPLCW spectra was less than 0.001 absorbance units. The portability, sampling, and optical characteristics of a MPLCW system provide significant enhancements for routine CDOM absorption measurements in a broad range of natural waters.

Picosecond absorption spectroscopy of self-trapped excitons and transient Ce states in LaBr3 and LaBr3:Ce

NASA Astrophysics Data System (ADS)

Li, Peiyun; Gridin, Sergii; Ucer, K. Burak; Williams, Richard T.; Menge, Peter R.

2018-04-01

Picosecond time-resolved optical absorption spectra induced by two-photon interband excitation of LaBr3 are reported. The spectra are similar in general characteristics to self-trapped exciton (STE) absorption previously measured in alkali halides and alkaline-earth halides. A broad ultraviolet absorption band results from excitation of the self-trapped hole within the STE. A series of infrared and red-visible bands results from excitation of the bound outer electron within the STE similar to bands found in alkali halides corresponding to different degrees of "off-center" relaxation. Induced absorption in cerium-doped LaBr3 after band-gap excitation of the host exhibits similar STE spectra, except it decays faster on the tens-of-picoseconds scale in proportion to the Ce concentration. This is attributed to dipole-dipole energy transfer from STE to Ce3 + dopant ions. The absorption spectra were also measured after direct excitation of the Ce3 + ions with sufficient intensity to drive two- and three-photon resonantly enhanced excitation. In this case, the spectrum attributed to STEs created adjacent to Ce3 + ions decays in 1 ps suggesting dipole-dipole transfer from the nearest-neighbor separation. A transient absorption band at 2.1 eV growing with Ce concentration is found and attributed to a charge-transfer excitation of the Ce3 +* excited state responsible for scintillation in LaBr3:Ce crystals. This study concludes that the energy transport from host to activator responsible for the scintillation of LaBr3:Ce proceeds by STE creation and dipole-dipole transfer more than by sequential trapping of holes and electrons on Ce3 + ions.

Optical filter selection for high confidence discrimination of strongly overlapping infrared chemical spectra.

PubMed

Major, Kevin J; Poutous, Menelaos K; Ewing, Kenneth J; Dunnill, Kevin F; Sanghera, Jasbinder S; Aggarwal, Ishwar D

2015-09-01

Optical filter-based chemical sensing techniques provide a new avenue to develop low-cost infrared sensors. These methods utilize multiple infrared optical filters to selectively measure different response functions for various chemicals, dependent on each chemical's infrared absorption. Rather than identifying distinct spectral features, which can then be used to determine the identity of a target chemical, optical filter-based approaches rely on measuring differences in the ensemble response between a given filter set and specific chemicals of interest. Therefore, the results of such methods are highly dependent on the original optical filter choice, which will dictate the selectivity, sensitivity, and stability of any filter-based sensing method. Recently, a method has been developed that utilizes unique detection vector operations defined by optical multifilter responses, to discriminate between volatile chemical vapors. This method, comparative-discrimination spectral detection (CDSD), is a technique which employs broadband optical filters to selectively discriminate between chemicals with highly overlapping infrared absorption spectra. CDSD has been shown to correctly distinguish between similar chemicals in the carbon-hydrogen stretch region of the infrared absorption spectra from 2800-3100 cm(-1). A key challenge to this approach is how to determine which optical filter sets should be utilized to achieve the greatest discrimination between target chemicals. Previous studies used empirical approaches to select the optical filter set; however this is insufficient to determine the optimum selectivity between strongly overlapping chemical spectra. Here we present a numerical approach to systematically study the effects of filter positioning and bandwidth on a number of three-chemical systems. We describe how both the filter properties, as well as the chemicals in each set, affect the CDSD results and subsequent discrimination. These results demonstrate the importance of choosing the proper filter set and chemicals for comparative discrimination, in order to identify the target chemical of interest in the presence of closely matched chemical interferents. These findings are an integral step in the development of experimental prototype sensors, which will utilize CDSD.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fransson, Thomas; Norman, Patrick; Coriani, Sonia

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as themore » state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this method.« less

High-resolution fluorescence imaging for red and far-red SIF retrieval at leaf and canopy scales

NASA Astrophysics Data System (ADS)

Albert, L.; Alonso, L.; Cushman, K.; Kellner, J. R.

2017-12-01

New commercial-off-the-shelf imaging spectrometers promise the combination of high spatial and spectral resolution needed to retrieve solar induced fluorescence (SIF) at multiple wavelengths for individual plants and even individual leaves from low-altitude airborne or ground-based platforms. Data from these instruments could provide insight into the status of the photosynthetic apparatus at scales of space and time not observable from high-altitude and space-based platforms, and could support calibration and validation activities of current and forthcoming space missions to quantify SIF (OCO-2, OCO-3, FLEX, and GEOCARB). High-spectral resolution enables SIF retrieval from regions of strong telluric absorption by molecular oxygen, and also within numerous solar Fraunhofer lines in atmospheric windows not obscured by oxygen or water absorptions. Here we evaluate algorithms for SIF retrieval using a commercial-off-the-shelf diffraction-grating imaging spectrometer with a spectral sampling interval of 0.05 nm and a FWHM < 0.2 nm throughout the 670 - 780 nm range. We demonstrate the tradeoffs between spatial resolution and signal-to-noise ratio using frame stacking and binning, and evaluate the consequences of these tradeoffs for SIF retrieval using three approaches: (1) oxygen-A and B retrieval; (2) retrieval based exclusively on solar Fraunhofer lines outside regions of telluric gas absorption; and (3) a retrieval based on the combination of these approaches. We evaluate the quality of these methods by comparison with coincident SIF spectra of leaves measured using a hand-held field spectrometer and short-pass filters that block incoming light at wavelengths > 650 or 700 nm. These filters enable a direct measurement of SIF emission > 650 or 700 nm that serves as a benchmark against which retrievals from reflectance spectra can be evaluated. We repeated this comparison between leaf-level SIF emission spectra and retrieved SIF emission spectra for leaves treated with drought stress and an herbicide (DCMU) that inhibits electron transfer from QA to QB of PSII.

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

PubMed

Fransson, Thomas; Coriani, Sonia; Christiansen, Ove; Norman, Patrick

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this method.

Mutation-Induced Changes in the Protein Environment and Site Energies in the (M)L214G Mutant of the Rhodobacter sphaeroides Bacterial Reaction Center.

PubMed

Jankowiak, Ryszard; Rancova, Olga; Chen, Jinhai; Kell, Adam; Saer, Rafael G; Beatty, J Thomas; Abramavicius, Darius

2016-08-18

This work focuses on the low-temperature (5 K) photochemical (transient) hole-burned (HB) spectra within the P870 absorption band, and their theoretical analysis, for the (M)L214G mutant of the photosynthetic Rhodobacter sphaeroides bacterial reaction center (bRC). To provide insight into system-bath interactions of the bacteriochlorophyll a (BChl a) special pair, i.e., P870, in the mutated bRC, the optical line shape function for the P870 band is calculated numerically. On the basis of the modeling studies, we demonstrate that (M)L214G mutation leads to a heterogeneous population of bRCs with modified (increased) total electron-phonon coupling strength of the special pair BChl a and larger inhomogeneous broadening. Specifically, we show that after mutation in the (M)L214G bRC a large fraction (∼50%) of the bacteriopheophytin (HA) chromophores shifts red and the 800 nm absorption band broadens, while the remaining fraction of HA cofactors retains nearly the same site energy as HA in the wild-type bRC. Modeling using these two subpopulations allowed for fits of the absorption and nonresonant (transient) HB spectra of the mutant bRC in the charge neutral, oxidized, and charge-separated states using the Frenkel exciton Hamiltonian, providing new insight into the mutant's complex electronic structure. Although the average (M)L214G mutant quantum efficiency of P(+)QA(-) state formation seems to be altered in comparison with the wild-type bRC, the average electron transfer time (measured via resonant transient HB spectra within the P870 band) was not affected. Thus, mutation in the vicinity of the electron acceptor (HA) does not tune the charge separation dynamics. Finally, quenching of the (M)L214G mutant excited states by P(+) is addressed by persistent HB spectra burned within the B band in chemically oxidized samples.

Fine wavelength id for tunable laser local oscillators. [sensing the absorption emission spectra of atmospheric gases

NASA Technical Reports Server (NTRS)

Savage, M. G.; Augeri, R. C.

1980-01-01

A wavelength ID device which consists of an electronic show that the etalon has a finesse F 30 which is maintainable for several days. These tests also demonstrate that the etalon system is capable of resonance frequency stability during similar time periods. With currently available coatings, this level of performance is achievable over an optical bandwidth delta lambda = 3 micrometers centered at lambda = 10 micrometers.

Gemini NorthNIRI Spectra of Pluto and Charon: Simultaneous Analysis of the Surface and Atmosphere

NASA Technical Reports Server (NTRS)

Cook, Jason C.; Cruikshank, Dale P.; Young, Leslie A.

2014-01-01

94035We report on our analysis of blended Pluto and Charon spectra over the wavelength range 1.4 to 2.5 m as obtained by the NIRI instrument on Gemini North on June 25-28, 2004. The data have a resolving power () around 1500 and a SNR around 200 per pixel. The observed blended spectra are compared to models that combine absorption from the solid ice on the surface using Hapke theory, and absorption from the gaseous atmosphere. We assume the spectrum is a combination of several spatially separate spectral units: a CH4-rich ice unit, a volatile unit (an intimate mixture of N2, CH4 and CO), and a Charon unit (H2O, ammonia hydrate and kaolinite). We test for the presence of hydrocarbons (i.e. C2H6) and nitriles (i.e. HCN) and examine cases where additional ices are present as either pure separate spatial units, mixed with the CH4-rich unit or part of the volatile unit. We conclude that 2-4 of Plutos surface is covered with pure-C2H6 and our identification of C2H6 is significantly strengthened when absorption due to gaseous CH4 is included. The inclusion of Plutos atmosphere demonstrates that low-resolution, high-SNR observations are capable of detecting Plutos atmosphere during a time when Plutos atmosphere may have been undergoing rapid changes (1988-2002) and no high-resolution spectra were obtained. In particular, we identify features at 1.665 and 2.317 m as the Q-branch of the 23 and 3+4 bands of gaseous CH4, respectively. The later band is also evident in many previously published spectra of Pluto. Our analysis finds it is unnecessary to include 13CO to explain the depth of the 2.405 m, which has been previously suggested to be a spectral blended with C2H6, but we cannot definitively rule out its presence. Funding for this work (Cook) has been provided by a NASA-PATM grant.

Optical Absorption Spectra of Nuclear Filters Modified by Deposition of Silver Nano- and Microparticles

NASA Astrophysics Data System (ADS)

Smolyanskii, A. S.; Kozlova, N. V.; Zheltova, A. V.; Aksyutina, A. S.; Shvedov, A. S.; Lakeev, S. G.

2015-07-01

Light scattering and interference patterns are studied in the optical absorption spectra of nuclear filters based on polyethylene terephthalate fi lms modifi ed by dry aerosol deposition of silver nano- and microparticles. Surface plasmon polaritons and localized plasmons formed by the passage of light through porous silver films are found to have an effect on the diffraction and interference modes. The thickness of silver nano- and microparticle coatings on the surface of the nuclear fi lters was determined from the shift in the interference patterns in the optical absorption spectra of the modified nuclear filters relative to the original nuclear filters. A correlation was found between the estimated coating thickness and the average surface roughness of the nuclear filters modified by layers of silver nano- and microparticles.

FIRST ULTRAVIOLET REFLECTANCE SPECTRA OF PLUTO AND CHARON BY THE HUBBLE SPACE TELESCOPE COSMIC ORIGINS SPECTROGRAPH: DETECTION OF ABSORPTION FEATURES AND EVIDENCE FOR TEMPORAL CHANGE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stern, S. A.; Spencer, J. R.; Shinn, A.

We have observed the mid-UV spectra of both Pluto and its large satellite, Charon, at two rotational epochs using the Hubble Space Telescope (HST) Cosmic Origins Spectrograph (COS) in 2010. These are the first HST/COS measurements of Pluto and Charon. Here we describe the observations and our reduction of them, and present the albedo spectra, average mid-UV albedos, and albedo slopes we derive from these data. These data reveal evidence for a strong absorption feature in the mid-UV spectrum of Pluto; evidence for temporal change in Pluto's spectrum since the 1990s is reported, and indirect evidence for a near-UV spectralmore » absorption on Charon is also reported.« less

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.

Spectroscopic identification of rare earth elements in phosphate glass

NASA Astrophysics Data System (ADS)

Devangad, Praveen; Tamboli, Maktum; Muhammed Shameem, K. M.; Nayak, Rajesh; Patil, Ajeetkumar; Unnikrishnan, V. K.; Santhosh, C.; Kumar, G. A.

2018-01-01

In this work, rare earth-doped phosphate glasses were synthesized and characterized using three different spectroscopic techniques. The absorption spectra of the prepared praseodymium (Pr) and samarium (Sm) doped glasses, recorded by a UV-VIS-NIR spectrophotometer, show the characteristic absorption bands of these elements. To confirm this inference, laser-induced fluorescence spectra of Pr and Sm were obtained at a laser excitation of 442 nm. Their emission bands are reported here. The elemental analysis of these samples was carried out using a laser-induced breakdown spectroscopy (LIBS) system. Characteristic emission lines of Pr and Sm have been identified and reported by the recorded LIBS spectra of glass samples. Results prove that using these three complimentary spectroscopic techniques (absorption, fluorescence and LIBS), we can meaningfully characterize rare earth-doped glass samples.

The Zugspitze radiative closure experiment for quantifying water vapor absorption over the terrestrial and solar infrared - Part 2: Accurate calibration of high spectral-resolution infrared measurements of surface solar radiation

NASA Astrophysics Data System (ADS)

Reichert, Andreas; Rettinger, Markus; Sussmann, Ralf

2016-09-01

Quantitative knowledge of water vapor absorption is crucial for accurate climate simulations. An open science question in this context concerns the strength of the water vapor continuum in the near infrared (NIR) at atmospheric temperatures, which is still to be quantified by measurements. This issue can be addressed with radiative closure experiments using solar absorption spectra. However, the spectra used for water vapor continuum quantification have to be radiometrically calibrated. We present for the first time a method that yields sufficient calibration accuracy for NIR water vapor continuum quantification in an atmospheric closure experiment. Our method combines the Langley method with spectral radiance measurements of a high-temperature blackbody calibration source (< 2000 K). The calibration scheme is demonstrated in the spectral range 2500 to 7800 cm-1, but minor modifications to the method enable calibration also throughout the remainder of the NIR spectral range. The resulting uncertainty (2σ) excluding the contribution due to inaccuracies in the extra-atmospheric solar spectrum (ESS) is below 1 % in window regions and up to 1.7 % within absorption bands. The overall radiometric accuracy of the calibration depends on the ESS uncertainty, on which at present no firm consensus has been reached in the NIR. However, as is shown in the companion publication Reichert and Sussmann (2016), ESS uncertainty is only of minor importance for the specific aim of this study, i.e., the quantification of the water vapor continuum in a closure experiment. The calibration uncertainty estimate is substantiated by the investigation of calibration self-consistency, which yields compatible results within the estimated errors for 91.1 % of the 2500 to 7800 cm-1 range. Additionally, a comparison of a set of calibrated spectra to radiative transfer model calculations yields consistent results within the estimated errors for 97.7 % of the spectral range.

Deep learning of quasar spectra to discover and characterize damped Lyα systems

NASA Astrophysics Data System (ADS)

Parks, David; Prochaska, J. Xavier; Dong, Shawfeng; Cai, Zheng

2018-05-01

We have designed, developed, and applied a convolutional neural network (CNN) architecture using multi-task learning to search for and characterize strong H I Lyα absorption in quasar spectra. Without any explicit modelling of the quasar continuum or application of the predicted line profile for Lyα from quantum mechanics, our algorithm predicts the presence of strong H I absorption and estimates the corresponding redshift zabs and H I column density N_{H I}, with emphasis on damped Lyα systems (DLAs, absorbers with N_{H I}≥ 2 × 10^{20} cm^{-2}). We tuned the CNN model using a custom training set of DLAs injected into DLA-free quasar spectra from the Sloan Digital Sky Survey (SDSS), data release 5 (DR5). Testing on a held-back validation set demonstrates a high incidence of DLAs recovered by the algorithm (97.4 per cent as DLAs and 99 per cent as an H I absorber with N_{H I}> 10^{19.5} cm^{-2}) and excellent estimates for zabs and N_{H I}. Similar results are obtained against a human-generated survey of the SDSS DR5 data set. The algorithm yields a low incidence of false positives and negatives but is challenged by overlapping DLAs and/or very high N_{H I} systems. We have applied this CNN model to the quasar spectra of SDSS DR7 and the Baryon Oscillation Spectroscopic Survey (data release 12) and provide catalogues of 4913 and 50 969 DLAs, respectively (including 1659 and 9230 high-confidence DLAs that were previously unpublished). This work validates the application of deep learning techniques to astronomical spectra for both classification and quantitative measurements.

Cavity ring-down spectroscopy in the liquid phase

NASA Astrophysics Data System (ADS)

Xu, Shucheng; Sha, Guohe; Xie, Jinchun

2002-02-01

A new application for cavity ring-down spectroscopic (CRDS) technique using a pulsed polarized light source has been developed in the absorption measurement of liquids for "colorless" organic compounds using both a single sample cell and double sample cells inserted in an optical cavity at Brewster angle. At present an experimental capability of measuring absorption coefficients as small as 2-5×10-7 cm-1 has been demonstrated by measurement of the absorption baselines. The first spectra for CRDS in the liquid phase, the C-H stretching fifth vibrational overtones of benzene in the pure liquid and hexane solution are obtained. The optical absorption length for liquids in both a single sample cell and double sample cells of 1 cm length is up to 900 cm due to multipass of light within an optical cavity. Compared to the thermal lens and optoacoustic spectroscopic techniques, the sensitivity for CRDS mainly depends on the optical absorption path of the sample (single passing path of the sample times multipass times), is not determined by the laser power and the length of the sample cell. The absolute absorption coefficient and band intensity for the sample are determined directly by the spectroscopy.

Correlations between Crystallite Size, Shape, Surface, and Infrared Spectra Using the Ti-C System

NASA Astrophysics Data System (ADS)

Kimura, Y.; Ikegami, A.; Kurumada, M.; Kamitsuji, K.; Kaito, C.

2004-06-01

TiC crystallites less than 10 nm in size showed an absorption feature at 14.3 μm. This 14.3 μm absorption was rarely seen in specimens ranging from bulk material to grains of 50 nm in size. The 14.3 μm feature was weakened as a result of the growth of TiC crystallites by heat treatment. When the carbide grains were covered with a carbon layer, the absorption peaks were considerably weakened, i.e., the absorption intensity depended on the grain surface state. A possible explanation is that the effects of size and shape on the spectra depend on the surface anisotropy.

Absorption and emission spectroscopic characteristics of dipterex and its molecularly imprinted recognition: A TD-DFT investigation

NASA Astrophysics Data System (ADS)

Cheng, Xueli; Li, Liqing; Zhao, Yanyun; Wang, Chang'an

2016-05-01

By using G09 program package, the absorption and fluorescence/phosphorescence spectra of dipterex were explored, and its spectroscopic characters were altered by methacrylic acid (MAA) as the imprinted molecule. The TD-DFT results revealed that: (1) All absorption and emission excitations of dipterex are assigned to the nσ∗ transition; (2) without MAA as imprinted molecule, one of the dipterex Csbnd Cl bonds is extended significantly and dipterex is almost destroyed in transition states; (3) dipterex is connected to methacrylic acid via two hydrogen bonds; (4) for the dipterex-MAA complex, the electronic excitation (ππ∗ excitation) in absorption spectra is dominated by the configuration HOMO → LUMO.

THz spectra of cortisone and the related medicine

NASA Astrophysics Data System (ADS)

Ma, Shihua; Ge, Min; Liu, Guifeng; Song, Xiyu; Zhang, Peng; Wang, Wenfeng

2009-07-01

THz-TDS are used to study four kinds of drug: cortisone, hydrocortisone, prednisone and prednisolone. The THz spectra of them are obtained and analyzed from 0.2 - 1.6 THz. The experimental results shows the four samples have the different THz spectra. Cortisone has a peak at 1.5 THz and a broad absorption peak at 0.96 THz, while hydrocortisone has a weak absorption peak that lies at 1.27 THz. At the same time the prednisone has the stronger absorption peaks than the others, and its two peaks shows at 1.24 THz and 1.5 THz. Prednisolone has a weak broad peak at 1.43 THz. The results of the theoretical calculation were performed using Gaussian 03 software with Density Functional Theory at the basis set of 6-31+G (d, p). The theoretical vibrational frequencies are compared with the experimental results, and the deviations are discussed. The THz spectra of the medicine show THz technique may be help to distinguish some different chemical bond and functional group.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Electronic structure of ZrX2 (X = Se, Te)

NASA Astrophysics Data System (ADS)

Shkvarin, A. S.; Merentsov, A. I.; Shkvarina, E. G.; Yarmoshenko, Yu. M.; Píš, I.; Nappini, S.; Titov, A. N.

2018-03-01

The electronic structure of the ZrX2 (X = Se, Te) compounds has been studied using photoelectron, resonant photoelectron and X-ray absorption spectroscopy, theoretical calculations of the X-ray absorption spectra, and density of electronic states. It was found that the absorption spectra and valence band spectra are influenced by the chalcogen type. The results of the multiplet calculation of the Zr4+ atom show that the change in the splitting in the crystal field, which is described by the 10Dq parameter, is due to the change in the ratio of covalent and ionic contributions to the chemical bond. The resonance band near the Fermi level in the valence band spectra is observed for ZrTe2 in the Zr 3p-4d resonant excitation mode. The extent of photon energy indicates the charge localization on the Zr atom. Similar resonance band for ZrSe2 is absent; it indicates the presence of a gap at the Fermi level.

Theoretical and experimental studies of the Nd3+ 4f3<-->4f25d transitions in monoclinic Nd:BaY2F8 crystal

NASA Astrophysics Data System (ADS)

Collombet, Annabelle; Guyot, Yannick; Joubert, Marie-France; Margerie, Jean; Moncorgé, Richard; Tkachuk, Alexandra

2004-11-01

Experimental spectroscopic results related to Nd3+-doped BaY2F8, are presented that include vacuum-ultraviolet ground-state absorption and excitation spectra as well as polarized emission and excited-state absorption spectra recorded in the near-ultraviolet spectral range at room and low temperatures. Calculations were performed to determine the positions of the 4f25d sublevels and the intensities and polarizations of the 4f3<-->4f25d optical transitions of the Nd3+ ions in the C2 symmetry sites of the biaxial host crystal. The simulated spectra agree well with the experimental spectra; in particular, the model that was used successfully reproduced the differences between the polarized spectra on one hand and between the spectra recorded at low and room temperatures on the other hand.

D-Glucosamine Conjugation Accelerates the Labeling Efficiency of Quantum Dots in Osteoblastic Cells

PubMed Central

Xie, Ming-Fang

2014-01-01

Quantum dots (QDs) are useful imaging tools in the medical and biological fields due to their optical properties, such as a high fluorescence intensity, remarkable resistance to photobleaching, broad absorption spectra, and narrow emission spectra. This is the first study to investigate the uptake of carboxylated QDs conjugated with D-glucosamine (core size: approximately 3 nm, final modified size: 20–30 nm) into cultured osteoblastic cells. The QDs attached to the cell surface and were transported into the cytoplasm within approximately three hours of culture, whose process was clearly demonstrated using specific fluorescent staining of the cell membrane. Although the intranuclear distribution was not observed, a dramatic decrease in the transfer of quantum dots into the cytoplasm was recognized after approximately seven days of culture. Other interesting phenomena include the escape of the quantum dots from lysosomes in the cytoplasm, as confirmed by the merging of both QD fluorescence and specific fluorescent staining of lysosomes in the cytoplasm. These findings suggest that D-glucosamine conjugation enhances proton absorption in acid organelles and promotes the lysosomal escape of QDs. PMID:24818156

Color tuning of photonic gel films by UV irradiation

NASA Astrophysics Data System (ADS)

Shin, Sung Eui; Kim, Su Young; Shin, Dong Myung

2010-02-01

Block copolymers have drawn increasing attention for fabricating functional nanomaterials due to their properties of self-assembly. In particular, photonic crystals hold promise for multiple optical applications. We prepared 1D photonic crystals with polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) lamellar films which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 57 kg /mol-b-57 kg/mol. The lamellar stacks, which are alternating layers of hydrophilic and hydrophobic moiety of PS-b-P2VP, are obtained by exposing the spin coated film under chloroform vapor. The band gaps of the lamellar films interestingly varied after immersion into the quaternizing solvents containing 5wt% of iodomethane solubilized in n-hexane. We demonstrate about the influence of UV light on those photonic gel films. To study of different properties of films, UV-visible absorption spectra were measured as a different UV irradiation time at swollen films with distilled water. The UV-visible maximum absorption spectra shifted by UV irradiation time. Dependent on the time of UV irradiations, we can change the photonic band gap.

Protein dynamics observed by tunable mid-IR quantum cascade lasers across the time range from 10ns to 1s.

PubMed

Schultz, Bernd-Joachim; Mohrmann, Hendrik; Lorenz-Fonfria, Victor A; Heberle, Joachim

2018-01-05

We have developed a spectrometer based on tunable quantum cascade lasers (QCLs) for recording time-resolved absorption spectra of proteins in the mid-infrared range. We illustrate its performance by recording time-resolved difference spectra of bacteriorhodopsin in the carboxylic range (1800-1700cm -1 ) and on the CO rebinding reaction of myoglobin (1960-1840cm -1 ), at a spectral resolution of 1cm -1 . The spectrometric setup covers the time range from 4ns to nearly a second with a response time of 10-15ns. Absorption changes as low as 1×10 -4 are detected in single-shot experiments at t>1μs, and of 5×10 -6 in kinetics obtained after averaging 100 shots. While previous time-resolved IR experiments have mostly been conducted on hydrated films of proteins, we demonstrate here that the brilliance of tunable quantum cascade lasers is superior to perform ns time-resolved experiments even in aqueous solution (H 2 O). Copyright © 2017 Elsevier B.V. All rights reserved.

Contrasting eigenvalue and singular-value spectra for lasing and antilasing in a PT -symmetric periodic structure

NASA Astrophysics Data System (ADS)

Ge, Li; Feng, Liang

2017-01-01

It has been proposed and demonstrated that lasing and coherent perfect absorption (CPA or "antilasing") coexist in parity-time (PT ) symmetric photonic systems. In this work we show that the spectral signature of such a CPA laser displayed by the singular value spectrum of the scattering matrix (S ) can be orders of magnitude wider than that displayed by the eigenvalue spectrum of S . Since the former reflects how strongly light can be absorbed or amplified and the latter announces the spontaneous symmetry breaking of S , these contrasting spectral signatures indicate that near perfect absorption and extremely strong amplification can be achieved even in the PT -symmetric phase of S , which is known for and defined by its flux-conserving eigenstates. We also show that these contrasting spectral signatures are accompanied by strikingly different sensitivities to disorder and imperfection, suggesting that the eigenvalue spectrum is potentially suitable for sensing and the singular value spectrum for robust switching. A differential light amplifier may also be devised based on these two spectra.

Quasiparticle Lifetime Broadening in Resonant X-ray Scattering of NH4NO3.

PubMed

Vinson, John; Jach, Terrence; Müller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

2016-07-15

It has been previously shown that two effects cause dramatic changes in the x-ray absorption and emission spectra from the N K edge of the insulating crystal ammonium nitrate. First, vibrational disorder causes major changes in the absorption spectrum, originating not only from the thermal population of phonons, but, significantly, from zero-point motion as well. Second, the anomalously large broadening ( ~ 4 eV) of the emission originating from nitrate σ states is due to unusually short lifetimes of quasiparticles in an otherwise extremely narrow band. In this work we investigate the coupling of these effects to core and valence excitons that are created as the initial x-ray excitation energy is progressively reduced toward the N edge. Using a GW /Bethe-Salpeter approach, we show the extent to which this anomalous broadening is captured by the GW approximation. The data and calculations demonstrate the importance that the complex self-energies (finite lifetimes) of valence bands have on the interpretation of emission spectra. We produce a scheme to explain why extreme lifetimes should appear in σ states of other similar compounds.

Concentrations of ethane (C2H6) in the lower stratosphere and upper troposphere and acetylene (C2H2) in the upper troposphere deduced from Atmospheric Trace Molecule Spectroscopy/Spacelab 3 spectra

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Russell, J. M., III; Zander, R.; Farmer, C. B.; Norton, R. H.

1987-01-01

This paper reports the results of the spectroscopic analysis of C2H6 and C2H2 absorption spectra obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument flown on the Shuttle as part of the Spacelab 3 mission. The spectra were recorded during sunset occultations occurring between 25 deg N and 31 deg N latitudes, yielding volume-mixing ratio profiles of C2H6 in the lower stratosphere and the upper troposphere, and an upper tropospheric profile of C2H2. These results compare well with previous in situ and remote sounding data obtained at similar latitudes and with model calculations. The results demonstrate the feasibility of the ATMOS instrument to sound the lower atmosphere from space.

Optical absorption and emission bands of Tm 3+ ions in calcium niobium gallium garnet crystal

NASA Astrophysics Data System (ADS)

Tsuboi, Taiju; Tanigawa, Masayuki; Shimamura, Kiyoshi

2000-12-01

Absorption spectra of Tm 3+ ions in Ca 3Nb 1.6875Ga 3.1875O 12 (CNGG) crystal have been investigated at various temperatures between 15 and 296 K. Luminescence spectra in a spectral region of 400-1750 nm are investigated under excitation into various excited states of Tm 3+ and the conduction band of CNGG at room temperature. The absorption and emission bands of Tm 3+ in CNGG are observed to be broader than those observed in other Tm 3+-doped crystals such as LiNbO 3. This is due to the disordered structure of CNGG. From the temperature dependence of absorption spectra, five Stark levels are derived for the 3H 6 ground state. The highest Stark level is found to be 351 cm -1 above the ground level. It is suggested that the low efficiency of the 2.02 μm lasing at room temperature is due to the narrow splitting of the Stark levels.

Atomic multiplets at the L2,3 edge of 3d transition metals and the ligand K edge in x-ray absorption spectroscopy of ionic systems

NASA Astrophysics Data System (ADS)

Olalde-Velasco, P.; Jiménez-Mier, J.; Denlinger, J.; Yang, W.-L.

2013-06-01

Experimental X-ray absorption spectra at the fluorine K and transition metal L2,3 absorption edges of the MF2 (M=Cr-Ni) family are presented. Ligand field calculations in D4h symmetry show very good agreement with the transition metal L2,3 XAS spectra. To successfully explain nominal Cr2+ L2,3 XAS spectrum in CrF2, the inclusion of Cr+ and Cr3+ was needed implying the presence of a disproportionation reaction. The multiplet calculations were then modified to remove the structure of the 2p hole in the calculated M 2p→3d absorption spectra. These results for the 3dn+1 states are in one to one correspondence with the leading edge structures found at the fluorine K edge. A direct comparison with the metal L2,3 edges also indicates that there is evidence of the metal multiplet at the fluorine K pre-edge structures.

Giant photocurrent enhancement by transition metal doping in quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Rimal, Gaurab; Pimachev, Artem K.; Yost, Andrew J.; Poudyal, Uma; Maloney, Scott; Wang, Wenyong; Chien, TeYu; Dahnovsky, Yuri; Tang, Jinke

2016-09-01

A huge enhancement in the incident photon-to-current efficiency of PbS quantum dot (QD) sensitized solar cells by manganese doping is observed. In the presence of Mn dopants with relatively small concentration (4 at. %), the photoelectric current increases by an average of 300% (up to 700%). This effect cannot be explained by the light absorption mechanism because both the experimental and theoretical absorption spectra demonstrate several times decreases in the absorption coefficient. To explain such dramatic increase in the photocurrent we propose the electron tunneling mechanism from the LUMO of the QD excited state to the Zn2SnO4 (ZTO) semiconductor photoanode. This change is due to the presence of the Mn instead of Pb atom at the QD/ZTO interface. The ab initio calculations confirm this mechanism. This work proposes an alternative route for a significant improvement of the efficiency for quantum dot sensitized solar cells.

Direct detection of saponins in crude extracts of soapnuts by FTIR.

PubMed

Almutairi, Meshari Saad; Ali, Muhammad

2015-01-01

Direct detection of saponins in soapnuts (Sapindus mukorossi) using Fourier transform infrared (FTIR) spectroscopy is investigated in this project. Potassium bromide powder was mixed with extracted powder of soapnuts and compressed to a thin pellet for examination process. The outcome of the FTIR spectra of saponin demonstrated characteristic triterpenoid saponin absorptions of OH, C = O, C-H, and C = C, while the glycoside linkages to the sapogenins were indicated by the absorptions of C-O. The significance of this study is that saponin absorption peaks are directly detectable in crude aqueous and 95% ethanol extracts of soapnuts powder using FTIR spectroscopy, thereby eliminating the need of further expensive and exhaustive purification steps. The extracts of soapnuts were screened for saponins along with controls by phytochemical tests, and advanced spectroscopic techniques such as ultra fast liquid chromatography and ultra performance liquid chromatography quadrupole-time of flight-mass spectrometry were also implemented to validate the saponins.

Demonstration of temperature imaging by H₂O absorption spectroscopy using compressed sensing tomography.

PubMed

An, Xinliang; Brittelle, Mack S; Lauzier, Pascal T; Gord, James R; Roy, Sukesh; Chen, Guang-Hong; Sanders, Scott T

2015-11-01

This paper introduces temperature imaging by total-variation-based compressed sensing (CS) tomography of H2O vapor absorption spectroscopy. A controlled laboratory setup is used to generate a constant two-dimensional temperature distribution in air (a roughly Gaussian temperature profile with a central temperature of 677 K). A wavelength-tunable laser beam is directed through the known distribution; the beam is translated and rotated using motorized stages to acquire complete absorption spectra in the 1330-1365 nm range at each of 64 beam locations and 60 view angles. Temperature reconstructions are compared to independent thermocouple measurements. Although the distribution studied is approximately axisymmetric, axisymmetry is not assumed and simulations show similar performance for arbitrary temperature distributions. We study the measurement error as a function of number of beams and view angles used in reconstruction to gauge the potential for application of CS in practical test articles where optical access is limited.

Photo-physical properties and triplet-triplet absorption of platinum(II) acetylides in solid PMMA matrices

NASA Astrophysics Data System (ADS)

Glimsdal, Eirik; Westlund, Robert; Lindgren, Mikael

2009-05-01

Because of their strong nonlinear optical properties, Platinum(II) acetylides are investigated as potential chromophores for optical power limiting (OPL) applications. The strong excited state absorption and efficient intersystem crossing to the triplet states in these materials are desired properties for good OPL performance. We recently reported on OPL and photo-physical properties of Pt(II)-acetylide chromophores in solution, modified with thiophenyl or triazole groups. [R. Westlund et al. J. Mater. Chem. 18, 166 (2008); E. Glimsdal et al. Proc. SPIE 6740, 67400M (2007)] The chromophores were later incorporated into poly(methyl-methacrylate) (PMMA) glasses. A variety of doped organic solids were prepared, reaching concentrations of up to 13 wt% of the guest molecule. Raman spectra of the doped solid devices proved that the chemical structure of the nonlinear dyes remains intact upon the polymerization of the solid matrix. Luminescence spectra confirm that the basic photo-physical properties (absorption, emission and inter-system crossing) observed for the solute molecules in THF are maintained also in the solid state. In particular, the phosphorescence lifetime stays in the order of μs to ms, just as in the oxygen evacuated liquid samples. Also, the wavelength dependence and time-dynamics of the triplet absorption spectra of the dyes, dissolved in THF solution and dispersed in solid PMMA matrices, were investigated and compared. Ground state UV absorption spectra between 300 and 420 nm have corresponding broad band visible triplet-triplet absorption between 400 and 800 nm. The triplet state extinction coefficients were determined to be in the order of 104 M-1cm-1.

[Absorption Characteristics and Simulation of LLM-105 in the Terahertz Range].

PubMed

Meng, Zeng-rui; Shang, Li-ping; Du, Yu; Deng, Hu

2015-07-01

2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), a novel explosive with high energy and low sensibility. In order to study the molecular structure characteristics of the explosive, the absorption spectra of LLM-105 in the frequency range of 0.2-2.4 THz were detected by terahertz time-domain spectroscopy (THz-TDS). The results showed that a number of characteristic absorption peaks with different intensity located at 1.27, 1.59, 2.00, 2.08, 2.20, 2.29 THz. The article also simulated the absorption spectra of LLM-105 molecular crystal within 0.2-2.5 THz region by using Materials Studio 6.0 software based on density functional theory (DFT), and the simulated results agreed well with the experimental data except for the peak at 2.29 THz, which verified theoretically the accuracy of the experimental data. In addition, the vibrational modes of the characteristic peaks in the experimental absorption spectra were analyzed and identified, the results showed that the forming of the characteristic absorption peaks and the molecular vibration were closely related, which further provided important laboratory and technology support for the study of the transformation of molecule structure of LLM-105. There was no simulated frequency agreed with the experimental absorption peak at 2.29 THz, which may be caused by the vibration of the crystal lattice or other reasons.

Subgap Absorption in Conjugated Polymers

DOE R&D Accomplishments Database

Sinclair, M.; Seager, C. H.; McBranch, D.; Heeger, A. J; Baker, G. L.

1991-01-01

Along with X{sup (3)}, the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter which will ultimately determine the utility of conjugated polymers in active integrated optical devices. With an absorptance sensitivity of < 10{sup {minus}5}, Photothermal Deflection Spectroscopy (PDS) is ideal for determining the absorption coefficients of thin films of transparent'' materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers poly(1,4-phenylene-vinylene) (and derivitives) and polydiacetylene-4BCMU in the spectral region from 0.55 eV to 3 eV. Our spectra show that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1 cm{sup {minus}1} to 10 cm{sup {minus}1}. In the region below 1 eV, overtones of C-H stretching modes were observed, indicating that further improvements in transparency in this spectral region might be achieved via deuteration of fluorination.

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

PubMed Central

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

2015-01-01

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

Assessing Pearl Quality Using Reflectance UV-Vis Spectroscopy: Does the Same Donor Produce Consistent Pearl Quality?

PubMed Central

Mamangkey, Noldy Gustaf F.; Agatonovic, Snezana; Southgate, Paul C.

2010-01-01

Two groups of commercial quality (“acceptable”) pearls produced using two donors, and a group of “acceptable” pearls from other donors were analyzed using reflectance UV-Vis spectrophotometry. Three pearls with different colors produced by the same donor showed different absorption spectra. Cream and gold colored pearls showed a wide absorption from 320 to about 460 nm, while there was just slight reflectance around 400 nm by the white pearl with a pink overtone. Cream and gold pearls reached a reflectance peak at 560 to 590 nm, while the white pearl with pink overtone showed slightly wider absorption in this region. Both cream and gold pearls showed an absorption peak after the reflectance peak, at about 700 nm for the cream pearl and 750 nm for the gold pearl. Two other pearls produced by the same donor (white with cream overtone and cream with various overtones) showed similar spectra, which differed in their intensity. One of these pearls had very high lustre and its spectrum showed a much higher percentage reflectance than the second pearl with inferior lustre. This result may indicate that reflectance is a useful quantitative indicator of pearl lustre. The spectra of two white pearls resulting from different donors with the same color nacre (silver) showed a reflectance at 260 nm, followed by absorption at 280 nm and another reflectance peak at 340 nm. After this peak the spectra for these pearls remained flat until a slight absorption peak around 700 nm. Throughout the visible region, all white pearls used in this study showed similar reflectance spectra although there were differences in reflectance intensity. Unlike the spectral results from white pearls, the results from yellow and gold pearls varied according to color saturation of the pearl. The results of this study show that similarities between absorption and reflectance spectra of cultured pearls resulting from the same saibo donor are negligible and could not be detected with UV-Vis spectrophotometry. Nevertheless, this technique could have a role to play in developing less subjective methods of assessing pearl quality and in further studies of the relationships between pearl quality and that of the donor and recipient oysters. PMID:20948903

Preliminary analysis of Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mineralogic mapping at sites in Nevada and Colorado

NASA Technical Reports Server (NTRS)

Kruse, Fred A.; Taranik, Dan L.; Kierein-Young, Kathryn S.

1988-01-01

Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data for sites in Nevada and Colorado were evaluated to determine their utility for mineralogical mapping in support of geologic investigations. Equal energy normalization is commonly used with imaging spectrometer data to reduce albedo effects. Spectra, profiles, and stacked, color-coded spectra were extracted from the AVIRIS data using an interactive analysis program (QLook) and these derivative data were compared to Airborne Imaging Spectrometer (AIS) results, field and laboratory spectra, and geologic maps. A feature extraction algorithm was used to extract and characterize absorption features from AVIRIS and laboratory spectra, allowing direct comparison of the position and shape of absorption features. Both muscovite and carbonate spectra were identified in the Nevada AVIRIS data by comparison with laboratory and AIS spectra, and an image was made that showed the distribution of these minerals for the entire site. Additional, distinctive spectra were located for an unknown mineral. For the two Colorado sites, the signal-to-noise problem was significantly worse and attempts to extract meaningful spectra were unsuccessful. Problems with the Colorado AVIRIS data were accentuated by the IAR reflectance technique because of moderate vegetation cover. Improved signal-to-noise and alternative calibration procedures will be required to produce satisfactory reflectance spectra from these data. Although the AVIRIS data were useful for mapping strong mineral absorption features and producing mineral maps at the Nevada site, it is clear that significant improvements to the instrument performance are required before AVIRIS will be an operational instrument.

Collision-Induced Infrared Absorption by Collisional Complexes in Dense Hydrogen-Helium Gas Mixtures at Thousands of Kelvin

NASA Astrophysics Data System (ADS)

Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

2011-06-01

The interaction-induced absorption by collisional pairs of H{_2} molecules is an important opacity source in the atmospheres of the outer planets and cool stars. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H{_2}-H{_2}, H{_2}-He, and H{_2}-H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin. Laboratory measurements of interaction-induced absorption spectra by H{_2} pairs exist only at room temperature and below. We show that our results reproduce these measurements closely, so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures. L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, "Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin", International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201 M. Abel, L. Frommhold, X. Li, and K. L. C. Hunt, "Collision-induced absorption by H{_2} pairs: From hundreds to thousands of Kelvin," J. Phys. Chem. A, published online, DOI: 10.1021/jp109441f L. Frommhold, M. Abel, F. Wang, M. Gustafsson, X. Li, and K. L. C. Hunt, "Infrared atmospheric emission and absorption by simple molecular complexes, from first principles", Mol. Phys. 108, 2265, 2010

IR Spectra of Different O2-Content Hemoglobin from Computational Study: Promising Detector of Hemoglobin Variant in Medical Diagnosis.

PubMed

Zhou, Su-Qin; Chen, Tu-Nan; Ji, Guang-Fu; Wang, En-Ren

2017-06-01

IR spectra of heme and different O 2 -content hemoglobin were studied by the quantum computation method at the molecule level. IR spectra of heme and different O 2 -content hemoglobin were quantificationally characterized from 0 to 100 THz. The IR spectra of oxy-heme and de-oxy-heme are obviously different at the frequency regions of 9.08-9.48, 38.38-39.78, 50.46-50.82, and 89.04-91.00 THz. At 24.72 THz, there exists the absorption peak for oxy-heme, whereas there is not the absorption peak for de-oxy-heme. Whether the heme contains Fe-O-O bond or not has the great influence on its IR spectra and vibration intensities of functional groups in the mid-infrared area. The IR adsorption peak shape changes hardly for different O 2 -content hemoglobin. However, there exist three frequency regions corresponding to the large change of IR adsorption intensities for containing-O 2 hemoglobin in comparison with de-oxy-hemoglobin, which are 11.08-15.93, 44.70-50.22, and 88.00-96.68 THz regions, respectively. The most differential values with IR intensity of different O 2 -content hemoglobin all exceed 1.0 × 10 4  L mol -1  cm -1 . With the increase of oxygen content, the absorption peak appears in the high-frequency region for the containing-O 2 hemoglobin in comparison with de-oxy-hemoglobin. The more the O 2 -content is, the greater the absorption peak is at the high-frequency region. The IR spectra of different O 2 -content hemoglobin are so obviously different in the mid-infrared region that it is very easy to distinguish the hemoglobin variant by means of IR spectra detector. IR spectra of hemoglobin from quantum computation can provide scientific basis and specific identification of hemoglobin variant resulting from different O 2 contents in medical diagnosis.

NARROW LINE ABSORPTION IN CACO3.

DTIC Science & Technology

CARBONATES), (*CALCIUM COMPOUNDS, (*ABSORPTION SPECTRA, CALCITE), (*CALCITE, RADIATION EFFECTS), ELECTRON PARAMAGNETIC RESONANCE, SINGLE CRYSTALS , NEUTRONS, X RAYS, GAMMA RAYS, IONS, CRYSTAL DEFECTS, PARAMAGNETIC RESONANCE.

Computer-Graphics Emulation of Chemical Instrumentation: Absorption Spectrophotometers.

ERIC Educational Resources Information Center

Gilbert, D. D.; And Others

1982-01-01

Describes interactive, computer-graphics program emulating behavior of high resolution, ultraviolet-visible analog recording spectrophotometer. Graphics terminal behaves as recording absorption spectrophotometer. Objective of the emulation is study of optimization of the instrument to yield accurate absorption spectra, including…

Structural properties and UV to NIR absorption spectra of metal-free phthalocyanine (H2Pc) thin films P. B. Thakor, P. N. Gajjar and A. R. Jani: Different reference systems in the study of structural properties of some simple liquid metals Shazia Bashir, M. S. Rafique, M. Khaleeq-ur-Rahman, Faizan-ul-Haq and B. R. Alvina: CO2 and Nd:YAG laser radiation induced damage in aluminium Smail Bougouffa: The study of atomic transitions by use of Numerov technique in schematic model

NASA Astrophysics Data System (ADS)

El-Nahass, M. M.; Farid, A. M.; Attia, A. A.; Ali, H. A. M.

The structural properties and absorption spectra of H2Pc thin films have been studied. The films used in these studies were thermally evaporated on glass/quartz substrates with thickness ranging from 60 to 460 nm. The XRD studies of H2Pc thin films showed that the as-deposited films have a-form with monoclinic system. The mean crystallite size (L), the dislocation density (d) and the strain (x) were evaluated. The molecular structure of H2Pc thin films is confirmed by analysis of (FTIR) spectra. The surface morphology of H2Pc thin films was examined by scanning electron microscope. The absorption spectra of H2Pc recorded in the UV - VIS - IR region for the as-deposited and the annealed thin films of different thickness have been analyzed. The spectra showed two absorption bands namely the Q-band and the Soret (B)-band. The Q-band shows its characteristic splitting (Davydove splitting) with DQ = 0.21 eV. Values of some important optical parameters, namely optical absorption coefficient (a¢), molar extinction coefficient (emolar), half-band-width (Dl), electronic dipole strength (q2) and oscillator strength (f) were calculated. The fundamental and the onset of the indirect energy gaps were also determined as 2.47 and 1.4 eV, respectively.

Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

DOE PAGES

Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.; ...

2016-11-02

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the firstmore » 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.« less

A Search for H I Lyα Counterparts to Ultrafast X-Ray Outflows

NASA Astrophysics Data System (ADS)

Kriss, Gerard A.; Lee, Julia C.; Danehkar, Ashkbiz

2018-06-01

Prompted by the H I Lyα absorption associated with the X-ray ultrafast outflow at ‑17,300 km s‑1 in the quasar PG 1211+143, we have searched archival UV spectra at the expected locations of H I Lyα absorption for a large sample of ultrafast outflows identified in XMM-Newton and Suzaku observations. Sixteen of the X-ray outflows have predicted H I Lyα wavelengths falling within the bandpass of spectra from either the Far Ultraviolet Spectroscopic Explorer or the Hubble Space Telescope, although none of the archival observations were simultaneous with the X-ray observations in which ultrafast X-ray outflows (UFOs) were detected. In our spectra broad features with FWHM of 1000 km s‑1 have 2σ upper limits on the H I column density of generally ≲2 × 1013 cm‑2. Using grids of photoionization models covering a broad range of spectral energy distributions (SEDs), we find that producing Fe XXVI Lyα X-ray absorption with equivalent widths >30 eV and associated H I Lyα absorption with {N}{{H}{{I}}}< 2× {10}13 {cm}}-2 requires total absorbing column densities {N}{{H}}> 5× {10}22 {cm}}-2 and ionization parameters log ξ ≳ 3.7. Nevertheless, a wide range of SEDs would predict observable H I Lyα absorption if ionization parameters are only slightly below peak ionization fractions for Fe XXV and Fe XXVI. The lack of Lyα features in the archival UV spectra indicates that the UFOs have very high ionization parameters, that they have very hard UV-ionizing spectra, or that they were not present at the time of the UV spectral observations owing to variability.

Variation of optical properties at Lucinda Jetty Coastal Observatory and its input into an optical model of coastal waters in Great Barrier Reef region.

NASA Astrophysics Data System (ADS)

Wozniak, Monika; Baird, Mark; Schroeder, Thomas; Clementson, Lesley; Jones, Emlyn

2017-04-01

The water column optical properties from an observation station located at the end of a 5.8 km long jetty in the coastal waters of the Great Barrier Reef World Heritage Area (18.52 S, 146.39 E) were studied. Due to the location of the Lucinda Jetty Coastal Observatory (LJCO), at the interface of large riverine nutrient and sediment sources and clear open ocean waters, it is an optically variable and interesting region. LJCO is the only Southern Hemisphere ocean colour validation site integrated into NASA's AERONET-OC global network of ground-based radiometers. LJCO has a 3 years long time series (2014-2016) of continuous in-water optical measurements of absorption (AC-S), scattering (AC-S) and backscattering (BB-9) spectra together with water-leaving radiance spectra (SeaPRISM) acquired above the water surface and concentration of water components (WQM). Further HPLC and spectrophotometrically-retrieved absorption and scattering were determined fortnightly. These detailed bio-optical observations are rarely available as a time-series for model assessment. We use these data to quantify the relationship between optical properties and water constituents and to developing a more accurate optical model for coastal, optically complex water like GBR model. Pigment analysis show that studied area is dominated by alternatively freshwater and oceanic phytoplankton species depending on weather condition, tides and season. Absorption spectra at 440 nm and 550 nm are dominated by detritus but also have a significant CDOM contribution, which influences reflectance values in that range of spectrum and negatively affects wavebands used in satellite and remote algorithms for water constituents. These emergent features are compared to the model outputs, demonstrating when the model produces accurate optical signals with realistic process representation.

Energy transfer mechanisms in layered 2D perovskites.

PubMed

Williams, Olivia F; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M

2018-04-07

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA) 2 (MA) n-1 [Pb n I 3n+1 ] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

Energy transfer mechanisms in layered 2D perovskites

NASA Astrophysics Data System (ADS)

Williams, Olivia F.; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M.

2018-04-01

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA)2(MA)n-1[PbnI3n+1] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

Tuning optical absorption and photoexcited recombination dynamics in La1-xSrxFeO3-δ through A-site substitution and oxygen vacancies

NASA Astrophysics Data System (ADS)

Smolin, Sergey; Scafetta, Mark; Choquette, Amber; Sfeir, Matthew; Baxter, Jason; May, Steven

We study optical absorption and recombination dynamics in La1-xSrxFeO3-δ thin films, uncovering the effects of tuning nominal Fe valence via A-site substitution and oxygen stoichiometry. Variable angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. These results demonstrate that while the static optical absorption is strongly dependent on Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics. Nsf: ECCS-1201957, MRI DMR-0922929, MRI DMR-1040166. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

UV laser long-path absorption spectroscopy

NASA Technical Reports Server (NTRS)

Dorn, Hans-Peter; Brauers, Theo; Neuroth, Rudolf

1994-01-01

Long path Differential Optical Absorption Spectroscopy (DOAS) using a picosecond UV laser as a light source was developed in our institute. Tropospheric OH radicals are measured by their rotational absorption lines around 308 nm. The spectra are obtained using a high resolution spectrograph. The detection system has been improved over the formerly used optomechanical scanning device by application of a photodiode array which increased the observed spectral range by a factor of 6 and which utilizes the light much more effectively leading to a considerable reduction of the measurement time. This technique provides direct measurements of OH because the signal is given by the product of the absorption coefficient and the OH concentration along the light path according to Lambert-Beers law. No calibration is needed. Since the integrated absorption coefficient is well known the accuracy of the measurement essentially depends on the extent to which the OH absorption pattern can be detected in the spectra. No interference by self generated OH radicals in the detection lightpath has been observed. The large bandwidth (greater than 0.15 nm) and the high spectral resolution (1.5 pm) allows absolute determination of interferences by other trace gas absorptions. The measurement error is directly accessible from the absorption-signal to baseline-noise ratio in the spectra. The applicability of the method strongly depends on visibility. Elevated concentrations of aerosols lead to considerable attenuation of the laser light which reduces the S/N-ratio. In the moderately polluted air of Julich, where we performed a number of OH measurement spectra. In addition absorption features of unidentified species were frequently detected. A quantitative deconvolution even of the known species is not easy to achieve and can leave residual structures in the spectra. Thus interferences usually increase the noise and deteriorate the OH detection sensitivity. Using diode arrays for sensitive absorption measurements some specific problems of those detectors have to be solved experimentally (i.e. fixed pattern noise, dark signal noise, nonuniform efficiency of individual elements, spatial sensitivity variations). In order to improve the low spatial resolution we performed laboratory studies using a multiple reflection cell to convert the long path technique to a real in situ point measurement. Under the conditions of field experiments in Julich residual absorbance signals at present are about 1.5x10(exp -4) corresponding to an OH detection sensitivity of 2x10(exp 6) OH/cm(exp 3) using a light path of 5.8 km. Total integration times for one measurement point vary between a few minutes and an hour.

Ground-Based VIS/NIR Reflectance Spectra of 25143 Itokawa: What Hayabusa will See and How Ground-Based Data can Augment Analyses

NASA Technical Reports Server (NTRS)

Vilas, Faith; Abell, P. A.; Jarvis, K. S.

2004-01-01

Planning for the arrival of the Hayabusa spacecraft at asteroid 25143 Itokawa includes consideration of the expected spectral information to be obtained using the AMICA and NIRS instruments. The rotationally-resolved spatial coverage the asteroid we have obtained with ground-based telescopic spectrophotometry in the visible and near-infrared can be utilized here to address expected spacecraft data. We use spectrophotometry to simulate the types of data that Hayabusa will receive with the NIRS and AMICA instruments, and will demonstrate them here. The NIRS will cover a wavelength range from 0.85 m, and have a dispersion per element of 250 Angstroms. Thus, we are limited in coverage of the 1.0 micrometer and 2.0 micrometer mafic silicate absorption features. The ground-based reflectance spectra of Itokawa show a large component of olivine in its surface material, and the 2.0 micrometer feature is shallow. Determining the olivine to pyroxene abundance ratio is critically dependent on the attributes of the 1.0- and 2.0 micrometer features. With a cut-off near 2,1 micrometer the longer edge of the 2.0- feature will not be obtained by NIRS. Reflectance spectra obtained using ground-based telescopes can be used to determine the regional composition around space-based spectral observations, and possibly augment the longer wavelength spectral attributes. Similarly, the shorter wavelength end of the 1.0 micrometer absorption feature will be partially lost to the NIRS. The AMICA filters mimic the ECAS filters, and have wavelength coverage overlapping with the NIRS spectral range. We demonstrate how merging photometry from AMICA will extend the spectral coverage of the NIRS. Lessons learned from earlier spacecraft to asteroids should be considered.

Calculation and Comparative Analysis of the IR Spectra of Homobrassinolide and (22S,23S)-Homobrassinolide

NASA Astrophysics Data System (ADS)

Andrianov, V. M.; Korolevich, M. V.

2015-09-01

Normal vibrational frequencies and absolute IR band intensities of the biologically active steroid phytohormones homobrassinolide and (22S,23S)-homobrassinolide were calculated in the framework of an original approach that combined classical analysis of normal modes using molecular mechanics with quantum-chemical estimation of the absolute intensities. IR absorption bands were interpreted based on a comparison of the experimental and theoretical absorption spectra. The impact of structural differences in the side chains of these molecules on the formation of their IR spectra in the region 1500-950 cm -1 was estimated.

Effect of pyridine on infrared absorption spectra of copper phthalocyanine.

PubMed

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

2008-02-01

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

Structural characterization of astaxanthin aggregates as revealed by analysis and simulation of optical spectra

NASA Astrophysics Data System (ADS)

Lu, Liping; Hu, Taoping; Xu, Zhigang

2017-10-01

Carotenoids can self-assemble in hydrated polar solvents to form J- or H-type aggregates, inducing dramatic changes in photophysical properties. Here, we measured absorption and emission spectra of astaxanthin in ethanol-water solution using ultraviolet-visible and fluorescence spectrometers. Two types of aggregates were distinguished in mixed solution at different water contents by absorption spectra. After addition of water, all probed samples immediately formed H-aggregates with maximum blue shift of 31 nm. In addition, J-aggregate was formed in 1:3 ethanol-water solution measured after an hour. Based on Frenkel exciton model, we calculated linear absorption and emission spectra of these aggregates to describe aggregate structures in solution. For astaxanthin, experimental results agreed well with the fitted spectra of H-aggregate models, which consisted of tightly packed stacks of individual molecules, including hexamers, trimers, and dimers. Transition moment of single astaxanthin in ethanol was obtained by Gaussian 09 program package to estimate the distance between molecules in aggregates. Intermolecular distance of astaxanthin aggregates ranges from 0.45 nm to 0.9 nm. Fluorescence analysis showed that between subbands, strong exciton coupling induced rapid relaxation of H-aggregates. This coupling generated larger Stokes shift than monomers and J-aggregates.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1996-01-10

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

Two-phase ultraviolet spectrophotometry of the pulsating white dwarf ZZ Piscium

NASA Technical Reports Server (NTRS)

Bond, H. E.; Kemper, E.; Grauer, A. D.; Holm, A. V.; Panek, R. J.; Schiffer, F. H., III

1985-01-01

Spectra of the pulsating white dwarf ZZ Psc (= G29-38) were obtained using the International Ultraviolet Explorer. By using a multiple-exposure technique in conjunction with simultaneous ground-based exposure-metering photometry, it was possible to obtain mean on-pulse and off-pulse spectra in the 1950-1310 A wavelength range. The ratio of the time-averaged on-pulse to off-pulse spectra is best fitted by a temperature variation that is in phase with the optical light variation. This result is consistent with the hypothesis that the observed variation is due to a high-order nonradial pulsation. Conventional ultraviolet spectra of ZZ Psc showed broad absorption features at 1390 and 1600 A. These features are also found in the spectra of the cool DA-type white dwarfs G226-29 and G67-23, and appear to increase in strength with decreasing temperature. A possible explanation for the 1600 A feature is absorption by the satellite band of resonance-broadened hydrogen Ly-alpha. Such absorption would also help explain a discrepancy between the observed pulsation amplitude shortward of 1650 A and the predicted amplitudes based on model atmospheres.

Electronic structures and population dynamics of excited states of xanthione and its derivatives

NASA Astrophysics Data System (ADS)

Fedunov, Roman G.; Rogozina, Marina V.; Khokhlova, Svetlana S.; Ivanov, Anatoly I.; Tikhomirov, Sergei A.; Bondarev, Stanislav L.; Raichenok, Tamara F.; Buganov, Oleg V.; Olkhovik, Vyacheslav K.; Vasilevskii, Dmitrii A.

2017-09-01

A new compound, 1,3-dimethoxy xanthione (DXT), has been synthesized and its absorption (stationary and transient) and luminescence spectra have been measured in n-hexane and compared with xanthione (XT) spectra. The pronounced broadening of xanthione vibronic absorption band related to the electronic transition to the second singlet excited state has been observed. Distinctions between the spectra of xanthione and its methoxy derivatives are discussed. Quantum chemical calculations of these compounds in the ground and excited electronic states have been accomplished to clarify the nature of electronic spectra changes due to modification of xanthione by methoxy groups. Appearance of a new absorption band of DXT caused by symmetry changes has been discussed. Calculations of the second excited state structure of xanthione and its methoxy derivatives confirm noticeable charge transfer (about 0.1 of the charge of an electron) from the methoxy group to thiocarbonyl group. Fitting of the transient spectra of XT and DXT has been fulfilled and the time constants of internal conversion S2 →S1 and intersystem crossing S1 →T1 have been determined. A considerable difference between the time constants of internal conversion S2 →S1 in XT and DXT is uncovered.

Fluid synthesis and structure of a new polymorphic modification of boron nitride

NASA Astrophysics Data System (ADS)

Pokropivny, V. V.; Smolyar, A. S.; Ovsiannikova, L. I.; Pokropivny, A. V.; Kuts, V. A.; Lyashenko, V. I.; Nesterenko, Yu. V.

2013-04-01

A new previously unknown phase of boron nitride with a hardness of 0.41-0.63 GPa has been pre-pared by the supercritical fluid synthesis. The presence of a new phase is confirmed by the X-ray spectra and IR absorption spectra, where new reflections and bands are distinguished. The fundamental reflection of the X-ray diffraction pattern is d = 0.286-0.291 nm, and the characteristic band in the infrared absorption spectrum is observed at 704 cm-1. The X-ray diffraction pattern and the experimental and theoretical infrared absorption spectra show that a new synthesized boron nitride phase can be a cluster crystal (space group 211) with a simple cubic lattice. Cage clusters of a fullerene-like morphology B24N24 with point symmetry O are arranged in lattice sites.

Infrared heterodyne spectroscopy of atmospheric ozone

NASA Technical Reports Server (NTRS)

Frerking, M. A.; Muehlner, D. J.

1977-01-01

The absorption spectrum of atmospheric ozone is measured within a 1/cm region at 1100/cm, using an IR heterodyne detector (spectrometer with CO2 local oscillator) developed for astronomical work. Absorption spectra obtained by passing radiation from the tunable diode laser through an absorption cell, heterodyne spectra of atmospheric ozone, and a predicted atmospheric spectrum are compared. Water vapor absorbing in the region of interest (1100/cm) is also considered. Preliminary results encourage the use of diode laser local oscillators in tunable heterodyne detector systems for spectroscopy of atmospheric ozone and remote high-resolution spectroscopy of atmospheric constituents and pollutants.

Universal formulation of excitonic linear absorption spectra in all semiconductor microstructures

NASA Astrophysics Data System (ADS)

Lefebvre, Pierre; Christol, Philippe; Mathieu, Henry

1995-01-01

We present a generalization of the well-known exciton absorption calculations of Elliott [Phys. Rev. 108, 1384 (1957)], in the 3-dimensional case, and of Shinada and Sugano [J. Phys. Soc. Japan 21, 1936 (1966)], for 2-dimensional media: We calculate the optical absorption spectra of bound and unbound exciton states, by using a metric space with a noninteger dimension α (1 < α), obtaining almost exactly the same theoretical lineshapes as those resulting from accurate but costly numerical approaches [Chuang et al. Phys. Rev. B, 43, 1500 (1991); Benner and Haug, Phys. Rev. B 47, 15750 (1993)].

Helium broadened propane absorption cross sections in the far-IR

NASA Astrophysics Data System (ADS)

Wong, A.; Billinghurst, B.; Bernath, P. F.

2017-09-01

Infrared absorption spectra for pure and He broadened propane have been recorded in the far-IR region (650-1300 cm-1) at the Canadian Light Source (CLS) facility using either the synchrotron or internal glowbar source depending on the required resolution. The measurements were made for 4 temperatures in the range 202-292 K and for 3 pressures of He broadening gas up to 100 Torr. Infrared absorption cross sections are derived from the spectra and the integrated cross sections are within 10 % of the corresponding values from the Pacific Northwest National Laboratory (PNNL) for all temperatures and pressures.

Infrared absorption cross sections of propane broadened by hydrogen

NASA Astrophysics Data System (ADS)

Wong, A.; Hargreaves, R. J.; Billinghurst, B.; Bernath, P. F.

2017-09-01

Fourier transform infrared absorption cross-sections of pure propane (C3H8) and propane broadened with H2 have been calculated from transmittance spectra recorded at temperatures from 292 K to 205 K. Transmittance spectra were recorded at the Canadian Light Source (CLS) Far-Infrared beamline, utilizing both the synchrotron source and the internal glowbar source. The absorption cross-sections have been calibrated to Pacific Northwest National Laboratory (PNNL) reference cross-sections of propane and can be used to interpret astronomical observations of giant planets such as Jupiter and Saturn as well as exoplanets.

Characterization by optical and magnetic spectroscopy of a synthesized SiO2 thin film used for radiation detector

NASA Astrophysics Data System (ADS)

Abdelaziz, T. D.; Ezz-Eldin, F. M.

2017-09-01

This work reports the synthesis and characterization of silica glass prepared by sol-gel procedure and finds out the effects of doses of gamma irradiation on the steps route of the heat-treated sample at 600 and 1100 °C. Combined characterizations of the glassy samples have been carried out by optical absorption and electron paramagnetic resonance. Also, FT infrared absorption spectra have been measured for both the heat-treated samples before and after gamma irradiation. Optical absorption spectra have identified an absorption band at 212-215 nm beside a broad band at 230-265 nm and the correlation of E' center with heat-treatment and gamma irradiation have been followed. FT infrared absorption spectra indicate the bands within near IR region representing the vibrational modes due to water, OH and SiOH within the wavenumber range 2500-3700 cm-1 are affected by heat treatment due to the elimination of organic residue and amount of OH and water. ESR investigations confirm the results obtained from optical and FTIR measurements. It is concluded from the collective data that sol-gel silica glass can serve as acceptable candidate for gamma-rays irradiator and gamma chamber dosimetry.

[The Study on the Far-FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms].

PubMed

Yang, Yu-ping; Fan, Li-jie; Cui, Bin; Chen, Gen-xiang; Zhang, Zhen-wei; Zhang, Cun-lin

2015-11-01

Far Fourier transform infrared spectroscopy (Far-FTIR) and terahertz time-domain spectroscopy (THz-TDS) were used to measure the fingerprint spectra of Azitromycin suspension, capsule, tablet and dispersible tablet under vacuum and nitrogen conditions, respectively. In the frequency range of 0.2-15 THz, highly resolved spectral features for Azitromycin suspension were measured and some minor differences were observed between domestic and exotic Azitromycin Suspension, such as linewidth broadening and additional peaks. As same time, for the domestic Azitromycin capsule, tablet and dispersible tablet, the absorption baselines in the range of 0.2-2.7 THz rise with the increase of frequency while absorption peaks become weaker due to the scattering of bigger particles and smaller amount of Azitromycin. Also, the additional peaks are caused by the absorption of filling materials. In parallel with the qualitative measurement, the THz absorption spectra for mixtures of polyethylene (PE) powders and exotic Azithomycin suspension with different concentrations were also measured. According to the linear correlation between the concentration and the absorption intensity, the concentration of effective component can be evaluated accurately. This means that THz-TDS method is suitable for the quality inspection and evaluation of the mixed Azithromycin system.

Optical absorption properties of Ge 2–44 and P-doped Ge nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Wei; Lu, Wen-Cai; Zhao, Li-Zhen

The optical absorption properties of non-crystalline and crystalline Ge nanoparticles with the sizes from ~ 2.5 to 15 Å have been studied at the B3LYP/6-31G level using time-dependent density functional theory. Hydrogen passivation and phosphorus doping on some selected Ge nanoparticles were also calculated. With the increase of cluster size, the optical absorption spectra of the non-crystalline Ge nanoparticles change from many peaks to a continuous broad band and at the same time exhibit a systematic red-shift. Doping phosphorus also causes the absorption spectra to shift toward the lower energy region for both non-crystalline and crystalline Ge nanoparticles. The non-crystallinemore » Ge nanoparticles are found to have stronger absorption in the visible region in comparison with the crystalline ones, regardless phosphorus doping.« less

Optical absorption properties of Ge 2–44 and P-doped Ge nanoparticles

DOE PAGES

Qin, Wei; Lu, Wen-Cai; Zhao, Li-Zhen; ...

2017-09-15

The optical absorption properties of non-crystalline and crystalline Ge nanoparticles with the sizes from ~ 2.5 to 15 Å have been studied at the B3LYP/6-31G level using time-dependent density functional theory. Hydrogen passivation and phosphorus doping on some selected Ge nanoparticles were also calculated. With the increase of cluster size, the optical absorption spectra of the non-crystalline Ge nanoparticles change from many peaks to a continuous broad band and at the same time exhibit a systematic red-shift. Doping phosphorus also causes the absorption spectra to shift toward the lower energy region for both non-crystalline and crystalline Ge nanoparticles. The non-crystallinemore » Ge nanoparticles are found to have stronger absorption in the visible region in comparison with the crystalline ones, regardless phosphorus doping.« less

A study of the effect of lithium oxide on the spectral properties of potassium-aluminoborate glass activated by chromium ions

NASA Astrophysics Data System (ADS)

Babkina, A. N.; Gorbachev, A. D.; Zyryanova, K. S.; Nikonorov, N. V.; Nuryev, R. K.; Stepanov, S. A.

2017-09-01

The results of designing and studying of potassium-aluminoborate glass activated by chromium and lithium ions are discussed. Changes in the absorption and luminescence spectra of glass after the isothermal treatment are demonstrated. X-ray diffraction data showed the presence of Li(Al7B4O17) and Cr2O3 nanocrystals with an average size of 20 and 15 nm, respectively. Analysis of the luminescence spectra showed that the Cr3+ ions are in a crystalline environment. The luminescence quantum yield was 20-50%, which indicates the prospects for using such materials as a basis for fiber amplifiers in information transmission systems and laser biomedical technologies.

Characteristics of InN epilayers grown with H2-assistance

NASA Astrophysics Data System (ADS)

Zhou, Jin; Li, Jinchai; Lu, Shiqiang; Kang, Junyong; Lin, Wei

2017-11-01

A series of InN films were grown on GaN-on-sapphire template with H2 pulse flow by metal organic vapor phase epitaxy. The scanning electron microscopy and atomic force microscopy observations demonstrate that the smooth surface has been achieved. The X-ray diffraction and Raman spectra measurements indicate that InN layers experience stronger accommodated compressive stress, resulting in a larger fraction of (002) oriented InN grains. On the basics of the first-principles calculations, these features can be understand as competition between N-penetrating effect with the assistance of the H atom and the etching effect of H2. Finally, the absorption spectra in conjunction with simulated results reveal that the band gap energy predominantly increase with increasing compressive strain.

Burst-mode manipulation of magnonic vortex crystals

NASA Astrophysics Data System (ADS)

Hänze, Max; Adolff, Christian F.; Weigand, Markus; Meier, Guido

2015-03-01

The manipulation of polarization states in 4 ×4 vortex crystals using sinusoidal magnetic field bursts is investigated by means of a broadband ferromagnetic-resonance setup. Magnetic field excitation with the proper amplitude and frequency allows tuning different polarization states, which are observed in the measured absorption spectra. The variation of the sinusoidal burst width consecutively identifies the time scale of the underlying process. A memorylike polarization state writing process is demonstrated on the submicrosecond time scale.

The green hemoproteins of bovine erythrocytes. II. Spectral, ligand-binding, and electrochemical properties.

PubMed

DeFilippi, L J; Hultquist, D E

1978-05-10

The two green hemoproteins isolated from bovine erythrocytes (form I and form II) have been characterized as to spectral, electrochemical, and chemical properties. The absorption spectra of the isolated hemoproteins are typical of high spin ferric states. Reduction of the hemoproteins yields high spin ferrohemoproteins. Complexation of the ferrohemoproteins with CO and the ferrihemoproteins with cyanide yields low spin complexes, demonstrating the presence of an exchangeable weak field ligand in both the ferrous and ferric states of the hemoproteins. The differences in position and intensity of the absorption peaks of the visible spectra allow the two forms to be distinguished from one another. The midpoint potential of forms I and II were found to be +0.075 and +0.019 V, respectively, at pH 6.4 and +0.038 and -0.005 V, respectively, at pH 7.0. This is consistent with the gaining of 1 proton/electron during the reduction. The Nernst plot reveals an unusual 0.5-electron transfer, whereas a quantitative titration demonstrates a 1-electron transfer. Form I binds cyanide more tightly than form II (KD of 84 and 252 micrometer, respectively). The observed spectral, electrochemical, and ligand-binding differences between forms I and II can be explained in terms of a greater electron-withdrawing ability of the side chains of the heme of form I relative to the heme of form II.

Spectroscopic Confirmation of Five Galaxy Clusters at z > 1.25 in the 2500 deg^2 SPT-SZ Survey

NASA Astrophysics Data System (ADS)

Khullar, Gourav; Bleem, Lindsey; Bayliss, Matthew; Gladders, Michael; South Pole Telescope (SPT) Collaboration

2018-06-01

We present spectroscopic confirmation of 5 galaxy clusters at 1.25 < z < 1.5, discovered in the 2500 deg2 South Pole Telescope Sunyaev-Zel’dovich (SPT-SZ) survey. These clusters, taken from a nearly redshift-independent mass-limited sample of clusters, have multi-wavelength follow-up imaging data from the X-ray to the near-IR, and currently form the most homogenous massive high-redshift cluster sample in existence. We briefly describe the analysis pipeline used on the low S/N spectra of these faint galaxies, and describing the multiple techniques used to extract robust redshifts from a combination of absorption-line (Ca II H&K doublet - λλ3934,3968Å) and emission-line ([OII] λλ3727,3729Å) spectral features. We present several ensemble analyses of cluster member galaxies that demonstrate the reliability of the measured redshifts. We also identify modest [OII] emission and pronounced CN and Hδ absorption in a composite stacked spectrum of 28 low S/N passive galaxy spectra with redshifts derived primarily from Ca II H&K features. This work increases the number of spectroscopically-confirmed SPT-SZ galaxy clusters at z > 1.25 from 2 to 7, further demonstrating the efficacy of SZ selection for the highest redshift massive clusters, and enabling further detailed study of these confirmed systems.

Microscopic Modeling of Intersubband Optical Processes in Type II Semiconductor Quantum Wells: Linear Absorption

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Kolokolov, Kanstantin I.; Ning, Cun-Zheng

2003-01-01

Linear absorption spectra arising from intersubband transitions in semiconductor quantum well heterostructures are analyzed using quantum kinetic theory by treating correlations to the first order within Hartree-Fock approximation. The resulting intersubband semiconductor Bloch equations take into account extrinsic dephasing contributions, carrier-longitudinal optical phonon interaction and carrier-interface roughness interaction which is considered with Ando s theory. As input for resonance lineshape calculation, a spurious-states-free 8-band kp Hamiltonian is used, in conjunction with the envelop function approximation, to compute self-consistently the energy subband structure of electrons in type II InAs/AlSb single quantum well structures. We demonstrate the interplay of nonparabolicity and many-body effects in the mid-infrared frequency range for such heterostructures.

Monomolecular layer of squarylium dye J aggregates exhibiting a femtosecond optical response of delocalized excitons

NASA Astrophysics Data System (ADS)

Furuki, Makoto; Pu, Lyong Sun; Sasaki, Fumio; Kobayashi, Shyunsuke; Tani, Toshiro

1998-05-01

We report on the demonstration of the femtosecond nonlinear optical response from a two-dimensional monomolecular layer of squarylium dye J aggregate at 5 °C. The formation of a monomolecular layer Langmuir film was achieved by spreading squarylium dye modified by two propyl and two hexyl groups at the air-water interface, which resulted in a very strong J band (o.d.=0.3) at 777 nm. The transient absorption spectra in a resonant pump-probe measurement showed a low absorption saturation power (9.7×106W/cm2) and an ultrafast response (300 fs), which are indicative of exciton delocalization over 18 molecules in this J aggregate, even at 5 °C.

Redshifts for Superliminal Candidates.II.

NASA Astrophysics Data System (ADS)

Vermeulen, R. C.; Taylor, G. B.; Readhead, A. C. S.; Browne, I. W. A.

1996-03-01

Spectra are presented for 24 compact extragalactic radio sources from complete samples being studied with VLBI. New emission line redshifts are given for 21 of the objects; in 7 of these we have also identified associated or intervening absorption line systems. In 1 other source there are absorption lines which provide a lower limit to the redshift. The remaining 2 objects have strong featureless spectra and are likely to be blazars.

Simultaneous measurement of displacement current and absorption spectra of Langmuir film

NASA Astrophysics Data System (ADS)

Xu, Xiaobin; Kubota, Tohru; Iwamoto, Mitsumasa

1995-07-01

A Maxwell-displacement-current measuring system coupled with the system used for the measurement of absorption spectra of monolayers on a water surface has been developed. Using this system, the displacement current and the absorbance across monolayers of squarylium dye at the air/water surface were detected. It was found that the change in J aggregate in the monolayers with monolayer compression was detectable using the system.

Infrared Reflectance Spectroscopy of Porous Silicas

NASA Astrophysics Data System (ADS)

Guiton, Theresa Anne

Fourier transform infrared (FTIR) specular reflectance spectroscopy was used to examine the fundamental phonon behavior of a series of porous silicas including porous Vycor, xerogels, aerogels, and colloidal solids. The spectra were deconvoluted using Kramers-Kronig analysis techniques, and the corresponding optical constants were determined via the Fresnel equations. The resulting spectra represent the first compilation of such data for low density silicas. The porous silicas revealed unique resonance modes for the imaginary dielectric function and energy loss function. A key distinction amongst the spectra was the change in the band shape of the antisymmetric Si-O-Si stretching modes. For instance, as the porosity level of the particulate systems increased, the peak maxima of the imaginary dielectric functions shifted to higher frequencies while the peak maxima of the associated energy loss function shifted to lower frequencies. In essence, with increasing porosity, the peak maxima of the imaginary dielectric functions and the energy loss functions were converging towards frequencies intermediate to the transverse optical and longitudinal optical modes of fused silica. A similar trend was not observed for the semi-continuous silica matrices. Maxwell Garnett effective medium modeling verified that these modes were a function of the porous microstructure and can be attributed to surface phonon modes. The effect of surface phonon modes was also evident in the absorption coefficient data. However, contrary to the traditional view that changes in the absorption spectra of porous silicas are strictly due to molecular structure, this study has demonstrated that variations can be attributed--both qualitatively and quantitatively--to electrostatic screening effects of finite particles.

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

NASA Astrophysics Data System (ADS)

Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

2014-10-01

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

Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

DOE PAGES

Wu, M.; Xin, Houlin L.; Wang, J. O.; ...

2018-04-24

Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, M.; Xin, Houlin L.; Wang, J. O.

Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

Path integral Monte Carlo study on the structure and absorption spectra of alkali atoms (Li, Na, K) attached to superfluid helium clusters

NASA Astrophysics Data System (ADS)

Nakayama, Akira; Yamashita, Koichi

2001-01-01

Path integral Monte Carlo calculations have been performed to investigate the microscopic structure and thermodynamic properties of the AkṡHeN (Ak=Li, Na, K,N⩽300) clusters at T=0.5 K. Absorption spectra which correspond to the 2P←2S transitions of alkali atoms are also calculated within a pairwise additive model, which employs diatomic Ak-He potential energy curves. The size dependences of the cluster structure and absorption spectra that show the influence of the helium cluster environment are examined in detail. It is found that alkali atoms are trapped in a dimple on the helium cluster's surface and that, from the asymptotic behavior, the AkṡHe300 cluster, at least semiquantitatively, mimics the local structure of experimentally produced large helium clusters in the vicinity of alkali atoms. We have successfully reproduced the overall shapes of the spectra and explained their features from a static and structural point of view. The positions, relative intensities, and line widths of the absorption maxima are calculated to be in moderate agreement with experiments [F. Stienkemeier, J. Higgins, C. Callegari, S. I. Kanorsky, W. E. Ernst, and G. Scoles, Z. Phys. D 38, 253 (1996)].

Fourier Transform Infrared Absorption Spectroscopy for Quantitative Analysis of Gas Mixtures at Low Temperatures for Homeland Security Applications.

PubMed

Meier, D C; Benkstein, K D; Hurst, W S; Chu, P M

2017-05-01

Performance standard specifications for point chemical vapor detectors are established in ASTM E 2885-13 and ASTM E 2933-13. The performance evaluation of the detectors requires the accurate delivery of known concentrations of the chemical target to the system under test. Referee methods enable the analyte test concentration and associated uncertainties in the analyte test concentration to be validated by independent analysis, which is especially important for reactive analytes. This work extends the capability of a previously demonstrated method for using Fourier transform infrared (FT-IR) absorption spectroscopy for quantitatively evaluating the composition of vapor streams containing hazardous materials at Acute Exposure Guideline Levels (AEGL) to include test conditions colder than laboratory ambient temperatures. The described method covers the use of primary reference spectra to establish analyte concentrations, the generation of secondary reference spectra suitable for measuring analyte concentrations under specified testing environments, and the use of additional reference spectra and spectral profile strategies to mitigate the uncertainties due to impurities and water condensation within the low-temperature (7 °C, -5 °C) test cell. Important benefits of this approach include verification of the test analyte concentration with characterized uncertainties by in situ measurements co-located with the detector under test, near-real-time feedback, and broad applicability to toxic industrial chemicals.

Spectral enhancement of leucocrystal violet treated footwear impression evidence in blood.

PubMed

Spence, Lindsay; Asmussen, Gary

2003-03-27

The results presented demonstrate the capacity for spectral enhancement to substantially improve the forensic examination of footwear impressions in blood treated with leucocrystal violet (LCV). The UV-Vis absorption spectra were generated of (i) an aqueous solution of leucocrystal violet, (ii) leucocrystal violet in 3% H(2)O(2), (iii) LCV working solution and (iv) whole blood added to LCV working solution. The resultant fluorescence emission spectra were subsequently generated (lambda(ex)=630nm, lambda(em)=661-900nm). The results indicate that the UV-Vis absorption spectra of an unbuffered solution of whole blood with LCV working solution produces a strong absorbance curve with a maxima at 630nm. Subsequent excitation at this wavelength and generation of the emission spectrum in the fluorescence mode indicates that a solution of whole blood added to LCV working solution is an extremely weak fluorophore. Therefore, to enable an adequate and timely enhancement of blood impression evidence treated with LCV utilising either visible fluorescence or infrared luminescence requires (i) selection of the most appropriate excitation wavelength (lambda(ex)) and emission wavelength (lambda(em)) with extremely narrow band pass filters, which in the absence of substrate matrix interference is excitation at 630nm producing the emission maxima at 665nm and (ii) a visual enhancement system such as a CCD colour IR video camera with image integration.

Evaluation of Parallel-Element, Variable-Impedance, Broadband Acoustic Liner Concepts

NASA Technical Reports Server (NTRS)

Jones, Michael G.; Howerton, Brian M.; Ayle, Earl

2012-01-01

Recent trends in aircraft engine design have highlighted the need for acoustic liners that provide broadband sound absorption with reduced liner thickness. Three such liner concepts are evaluated using the NASA normal incidence tube. Two concepts employ additive manufacturing techniques to fabricate liners with variable chamber depths. The first relies on scrubbing losses within narrow chambers to provide acoustic resistance necessary for sound absorption. The second employs wide chambers that provide minimal resistance, and relies on a perforated sheet to provide acoustic resistance. The variable-depth chambers used in both concepts result in reactance spectra near zero. The third liner concept employs mesh-caps (resistive sheets) embedded at variable depths within adjacent honeycomb chambers to achieve a desired impedance spectrum. Each of these liner concepts is suitable for use as a broadband sound absorber design, and a transmission line model is presented that provides good comparison with their respective acoustic impedance spectra. This model can therefore be used to design acoustic liners to accurately achieve selected impedance spectra. Finally, the effects of increasing the perforated facesheet thickness are demonstrated, and the validity of prediction models based on lumped element and wave propagation approaches is investigated. The lumped element model compares favorably with measured results for liners with thin facesheets, but the wave propagation model provides good comparisons for a wide range of facesheet thicknesses.

Fourier Transform Infrared Absorption Spectroscopy for Quantitative Analysis of Gas Mixtures at Low Temperatures for Homeland Security Applications

PubMed Central

Meier, D.C.; Benkstein, K.D.; Hurst, W.S.; Chu, P.M.

2016-01-01

Performance standard specifications for point chemical vapor detectors are established in ASTM E 2885-13 and ASTM E 2933-13. The performance evaluation of the detectors requires the accurate delivery of known concentrations of the chemical target to the system under test. Referee methods enable the analyte test concentration and associated uncertainties in the analyte test concentration to be validated by independent analysis, which is especially important for reactive analytes. This work extends the capability of a previously demonstrated method for using Fourier transform infrared (FT-IR) absorption spectroscopy for quantitatively evaluating the composition of vapor streams containing hazardous materials at Acute Exposure Guideline Levels (AEGL) to include test conditions colder than laboratory ambient temperatures. The described method covers the use of primary reference spectra to establish analyte concentrations, the generation of secondary reference spectra suitable for measuring analyte concentrations under specified testing environments, and the use of additional reference spectra and spectral profile strategies to mitigate the uncertainties due to impurities and water condensation within the low-temperature (7 °C, −5 °C) test cell. Important benefits of this approach include verification of the test analyte concentration with characterized uncertainties by in situ measurements co-located with the detector under test, near-real-time feedback, and broad applicability to toxic industrial chemicals. PMID:28090126

Model-independent Exoplanet Transit Spectroscopy

NASA Astrophysics Data System (ADS)

Aronson, Erik; Piskunov, Nikolai

2018-05-01

We propose a new data analysis method for obtaining transmission spectra of exoplanet atmospheres and brightness variation across the stellar disk from transit observations. The new method is capable of recovering exoplanet atmosphere absorption spectra and stellar specific intensities without relying on theoretical models of stars and planets. We simultaneously fit both stellar specific intensity and planetary radius directly to transit light curves. This allows stellar models to be removed from the data analysis. Furthermore, we use a data quality weighted filtering technique to achieve an optimal trade-off between spectral resolution and reconstruction fidelity homogenizing the signal-to-noise ratio across the wavelength range. Such an approach is more efficient than conventional data binning onto a low-resolution wavelength grid. We demonstrate that our analysis is capable of reproducing results achieved by using an explicit quadratic limb-darkening equation and that the filtering technique helps eliminate spurious spectral features in regions with strong telluric absorption. The method is applied to the VLT FORS2 observations of the exoplanets GJ 1214 b and WASP-49 b, and our results are in agreement with previous studies. Comparisons between obtained stellar specific intensity and numerical models indicates that the method is capable of accurately reconstructing the specific intensity. The proposed method enables more robust characterization of exoplanetary atmospheres by separating derivation of planetary transmission and stellar specific intensity spectra (that is model-independent) from chemical and physical interpretation.

A multimode vibronic treatment of absorption, resonance Raman, and hyper-Rayleigh scattering of excitonically coupled molecular dimers

NASA Astrophysics Data System (ADS)

Myers Kelley, Anne

2003-08-01

The linear absorption spectra, resonance Raman excitation profiles and depolarization dispersion curves, and hyper-Rayleigh scattering profiles are calculated for excitonically coupled homodimers of a model electron donor-acceptor "push-pull" conjugated chromophore as a function of dimer geometry. The vibronic eigenstates of the dimer are calculated by diagonalizing the matrix of transition dipole couplings among the vibronic transitions of the constituent monomers. The absorption spectra show the usual red- or blueshifted transitions for J-type or H-type dimers, respectively. When the electronic coupling is large compared with the vibronic width of the monomer spectrum, the dimer absorption spectra exhibit simple Franck-Condon progressions having reduced vibronic intensities compared with the monomer, and the resonance Raman excitation profiles are shifted but otherwise only weakly perturbed. When the coupling is comparable to the vibronic width, the H-dimer absorption spectra exhibit irregular vibronic frequency spacings and intensity patterns and the effects on the Raman excitation profiles are larger. There is strong dispersion in the Raman depolarization ratios for dimer geometries in which both transitions carry oscillator strength. The first hyperpolarizabilities are somewhat enhanced in J-dimers and considerably reduced in H-dimers. These effects on the molecular β will amplify the effects of dimerization on the ground-state dipole moment in electro-optic materials formed from chromophore-doped polymers that must be electric field poled to obtain the net alignment needed for a macroscopic χ(2).

Reconstruction of the absorption spectrum of an object spot from the colour values of the corresponding pixel(s) in its digital image: the challenge of algal colours.

PubMed

Coltelli, Primo; Barsanti, Laura; Evangelista, Valter; Frassanito, Anna Maria; Gualtieri, Paolo

2016-12-01

A novel procedure for deriving the absorption spectrum of an object spot from the colour values of the corresponding pixel(s) in its image is presented. Any digital image acquired by a microscope can be used; typical applications are the analysis of cellular/subcellular metabolic processes under physiological conditions and in response to environmental stressors (e.g. heavy metals), and the measurement of chromophore composition, distribution and concentration in cells. In this paper, we challenged the procedure with images of algae, acquired by means of a CCD camera mounted onto a microscope. The many colours algae display result from the combinations of chromophores whose spectroscopic information is limited to organic solvents extracts that suffers from displacements, amplifications, and contraction/dilatation respect to spectra recorded inside the cell. Hence, preliminary processing is necessary, which consists of in vivo measurement of the absorption spectra of photosynthetic compartments of algal cells and determination of spectra of the single chromophores inside the cell. The final step of the procedure consists in the reconstruction of the absorption spectrum of the cell spot from the colour values of the corresponding pixel(s) in its digital image by minimization of a system of transcendental equations based on the absorption spectra of the chromophores under physiological conditions. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.