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Sample records for absorption spectroscopy ir

  1. Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) in low pressure flames

    SciTech Connect

    Scherer, J.J.; Rakestraw, D.J.

    1996-12-31

    The authors have employed Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) as a diagnostic tool for combustion chemistry studies. High resolution rovibrational absorption spectra have been obtained in low pressure laminar flames in the mid-infrared employing a pulsed single mode optical parametric oscillator (OPO) laser system. The high sensitivity and generality of IR-CRLAS for combustion studies is demonstrated in a variety of flames and is shown to be robust even in sooting environments with high temperature gradients. The ability to obtain spatially resolved data is also demonstrated in one dimensional laminar flame studies. These preliminary results indicate the potential of IR-CRLAS as a combustion diagnostic which is capable of obtaining absolute concentrations of reactants, intermediates, and products simultaneously within a narrow spectral region. In this demonstration, two information rich mid-infrared spectral regions (1.6 and 3-4 microns) have been probed at Doppler-limited resolution with an effective laser bandwidth of < 0.007 cm{sup -1}.

  2. Intracavity laser absorption spectroscopy using mid-IR quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Medhi, G.; Muravjov, A. V.; Saxena, H.; Fredricksen, C. J.; Brusentsova, T.; Peale, R. E.; Edwards, O.

    2011-06-01

    Intracavity Laser Absorption Spectroscopy (ICLAS) at IR wavelengths offers an opportunity for spectral sensing with sufficient sensitivity to detect vapors of low vapor pressure compounds such as explosives. Reported here are key enabling technologies for this approach, including multi-mode external-cavity quantum cascade lasers and a scanning Fabry-Perot spectrometer to analyze the laser mode spectrum in the presence of a molecular intracavity absorber. Reported also is the design of a compact integrated data acquisition and control system. Applications include military and commercial sensing for threat compounds, chemical gases, biological aerosols, drugs, and banned or invasive plants or animals, bio-medical breath analysis, and terrestrial or planetary atmosphere science.

  3. X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

    NASA Astrophysics Data System (ADS)

    Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

    2016-03-01

    We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1‑xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks.

  4. X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4.

    PubMed

    Sohn, C H; Cho, Deok-Yong; Kuo, C-T; Sandilands, L J; Qi, T F; Cao, G; Noh, T W

    2016-01-01

    We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1-xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)-(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

  5. X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

    PubMed Central

    Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

    2016-01-01

    We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

  6. Subpicosecond IR transient absorption spectroscopy: measurement of internal conversion rates in DABCO vapor

    NASA Astrophysics Data System (ADS)

    Glownia, J. H.; Misewich, J.; Sorokin, P. P.

    1987-09-01

    An apparatus combining subpicosecond 248.5 nm pump pulses with a time-resolved subpicosecond broadband infrared absorption spectroscopy probe has been utilized to measure an internal conversion rate in 1,4-diazabicyclo[2.2.2]octane vapor. A subpicosecond (⪅ 500 fs) internal conversion rate has been determined.

  7. Formation of host-guest complexes on gold surface investigated by surface-enhanced IR absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Inokuchi, Yoshiya; Mizuuchi, Takahiro; Ebata, Takayuki; Ikeda, Toshiaki; Haino, Takeharu; Kimura, Tetsunari; Guo, Hao; Furutani, Yuji

    2014-01-01

    We apply surface-enhanced infrared absorption (SEIRA) spectroscopy to host-guest complexes in liquid phase to examine the structural change in the complex formation. Two thiol derivatives of 18-crown-6 (18C6) are chemisorbed on a gold surface, and aqueous solutions of MCl salts (M = Li, Na, K, Rb, and Cs) are put to form M+·18C6 complexes. Infrared spectra of these complexes in the 900-2000 cm-1 region are obtained by SEIRA spectroscopy. The observed IR spectra show noticeable peaks due to the complex formation, demonstrating that SEIRA spectroscopy will be a powerful method to investigate the structure of host-guest complexes in supramolecular chemistry.

  8. Hot Carrier Dynamics in the X Valley in Si and Ge Measured by Pump-IR-Probe Absorption Spectroscopy

    NASA Technical Reports Server (NTRS)

    Wang, W. B.; Cavicchia, M. A.; Alfano, R. R.

    1996-01-01

    Si is the semiconductor of choice for nanoelectronic roadmap into the next century for computer and other nanodevices. With growing interest in Si, Ge, and Si(sub m)Ge(sub n) strained superlattices, knowledge of the carrier relaxation processes in these materials and structures has become increasingly important. The limited time resolution for earlier studies of carrier dynamics in Ge and Si, performed using Nd:glass lasers, was not sufficient to observe the fast cooling processes. In this paper, we present a direct measurement of hot carrier dynamics in the satellite X valley in Si and Ge by time-resolved infrared(IR) absorption spectroscopy, and show the potential of our technique to identify whether the X valley is the lowest conduction valley in semiconductor materials and structures.

  9. Rapid screening and identification of illicit drugs by IR absorption spectroscopy and gas chromatography

    NASA Astrophysics Data System (ADS)

    Mengali, Sandro; Liberatore, Nicola; Luciani, Domenico; Viola, Roberto; Cardinali, Gian Carlo; Elmi, Ivan; Poggi, Antonella; Zampolli, Stefano; Biavardi, Elisa; Dalcanale, Enrico; Bonadio, Federica; Delemont, Olivier; Esseiva, Pierre; Romolo, Francesco S.

    2013-01-01

    Analytical instruments based on InfraRed Absorption Spectroscopy (IRAS) and Gas Chromatography (GC) are today available only as bench-top instrumentation for forensic labs and bulk analysis. Within the 'DIRAC' project funded by the European Commission, we are developing an advanced portable sensor, that combines miniaturized GC as its key chemical separation tool, and IRAS in a Hollow Fiber (HF) as its key analytical tool, to detect and recognize illicit drugs and key precursors, as bulk and as traces. The HF-IRAS module essentially consists of a broadly tunable External Cavity (EC) Quantum Cascade Laser (QCL), thermo-electrically cooled MCT detectors, and an infrared hollow fiber at controlled temperature. The hollow fiber works as a miniaturized gas cell, that can be connected to the output of the GC column with minimal dead volumes. Indeed, the module has been coupled to GC columns of different internal diameter and stationary phase, and with a Vapour Phase Pre-concentrator (VPC) that selectively traps target chemicals from the air. The presentation will report the results of tests made with amphetamines and precursors, as pure substances, mixtures, and solutions. It will show that the sensor is capable of analyzing all the chemicals of interest, with limits of detection ranging from a few nanograms to about 100-200 ng. Furthermore, it is suitable to deal with vapours directly trapped from the headspace of a vessel, and with salts treated in a basic solution. When coupled to FAST GC columns, the module can analyze multi-components mixes in less than 5 minutes.

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  11. Probing photochemical transformations at TiO{sub 2}/Pt and TiO{sub 2}/Ir interfaces using x-ray absorption spectroscopy

    SciTech Connect

    Lahiri, Debdutta; Subramanian, V.; Bunker, Bruce A.; Kamat, Prashant V.

    2006-05-28

    Structural transformations at the TiO{sub 2}/Pt and TiO{sub 2}/Ir interfaces during UV-irradiation have been probed by X-ray absorption spectroscopy. Oxidation by the photogenerated holes results in the intercalation of Pt and Ir into the Titania matrix. The structural transformations observed with Pt and Ir nanoparticles anchored on TiO{sub 2} is different than the clustering of gold atoms observed in the TiO{sub 2}/Au system. Implications of such structural transformations on the photocatalytic activity of semiconductor photocatalyts are discussed.

  12. High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

    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

    2016-01-01

    We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

  13. Activation and deactivation of a robust immobilized Cp*Ir-transfer hydrogenation catalyst: a multielement in situ X-ray absorption spectroscopy study.

    PubMed

    Sherborne, Grant J; Chapman, Michael R; Blacker, A John; Bourne, Richard A; Chamberlain, Thomas W; Crossley, Benjamin D; Lucas, Stephanie J; McGowan, Patrick C; Newton, Mark A; Screen, Thomas E O; Thompson, Paul; Willans, Charlotte E; Nguyen, Bao N

    2015-04-01

    A highly robust immobilized [Cp*IrCl2]2 precatalyst on Wang resin for transfer hydrogenation, which can be recycled up to 30 times, was studied using a novel combination of X-ray absorption spectroscopy (XAS) at Ir L3-edge, Cl K-edge, and K K-edge. These culminate in in situ XAS experiments that link structural changes of the Ir complex with its catalytic activity and its deactivation. Mercury poisoning and "hot filtration" experiments ruled out leached Ir as the active catalyst. Spectroscopic evidence indicates the exchange of one chloride ligand with an alkoxide to generate the active precatalyst. The exchange of the second chloride ligand, however, leads to a potassium alkoxide-iridate species as the deactivated form of this immobilized catalyst. These findings could be widely applicable to the many homogeneous transfer hydrogenation catalysts with Cp*IrCl substructure. PMID:25768298

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

    PubMed

    Radney, James G; Zangmeister, Christopher D

    2015-07-21

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

  15. IR, NIR, and UV Absorption Spectroscopy of C60(2+) and C60(3+) in Neon Matrixes.

    PubMed

    Kern, Bastian; Strelnikov, Dmitry; Weis, Patrick; Böttcher, Artur; Kappes, Manfred M

    2014-02-01

    C60(2+) and C60(3+) were produced by electron-impact ionization of sublimed C60 and charge-state-selectively codeposited onto a gold mirror substrate held at 5 K together with neon matrix gas containing a few percent of the electron scavengers CO2 or CCl4. This procedure limits charge-changing of the incident fullerene projectiles during matrix isolation. IR, NIR, and UV-vis spectra were then measured. Ten IR absorptions of C60(2+) were identified. C60(3+) was observed to absorb in the NIR region close to the known vibronic bands of C60(+). UV spectra of C60, C60(+), and C60(2+) were almost indistinguishable, consistent with a plasmon-like nature of their UV absorptions. The measurements were supported by DFT and TDDFT calculations, revealing that C60(2+) has a singlet D5d ground state whereas C60(3+) forms a doublet of Ci symmetry. The new results may be of interest regarding the presence of C60(2+) and C60(3+) in space. PMID:26276592

  16. Absorption Spectroscopy and Imaging from the Visible through Mid-IR with 20 nm Resolution Using AFM probes

    NASA Astrophysics Data System (ADS)

    Centrone, Andrea

    2015-03-01

    Correlated nanoscale composition and optical property maps are important to engineer nanomaterials in applications ranging from photovoltaics to sensing and therapeutics. Wavelengths (λs) from the visible to near-IR probe electronic transitions in materials, providing information regarding band gap and defects while light in mid-IR probes vibrational transitions and provide chemical composition. However, light diffraction limits the lateral resolution of conventional micro-spectroscopic techniques to approximately λ/2, which is insufficient to image nanomaterials. Additionally, the λ-dependent resolution impedes direct comparison of spectral maps from different spectral ranges. Photo Thermal Induced Resonance (PTIR) is a novel technique that circumvents light diffraction by employing an AFM tip as a local detector for measuring light absorption with λ-independent nanoscale resolution. Our PTIR setup combines an AFM microscope with three lasers providing λ-tunability from 500 nm to 16000 nm continuously. The AFM tip transduces locally the sample thermal expansion induced by light absorption into large cantilever oscillations. Local absorption spectra (electronic or vibrational) and maps are obtained recording the amplitude of the tip deflection as a function of λ and position, respectively. The working principles of the PTIR technique will be described first, and nano-patterned polymer samples will be used to evaluate its lateral resolution, sensitivity and linearity. Results show that the PTIR signal intensity is proportional to the local absorbed energy suggesting applicability of this technique for quantitative chemical analysis at nanoscale, at least for thin (less than 1000 nm thick) samples. Additionally, a λ-independent resolution as high as 20 nm is demonstrated across the whole spectral range. In the second part of the talk, PTIR will be applied to image the dark plasmonic resonance of gold Asymmetric Split Ring Resonators (A-SRRs) in the mid-IR

  17. An investigation of catalytic active phase-support interactions by IR, NMR and x-ray absorption spectroscopies

    SciTech Connect

    Haller, G.L.

    1992-09-01

    Active catalytic phases (metal, mixed metals, oxide or mixed oxides) interacting with oxide support on which the active phase is dispersed can affect the percentage exposed, the morphology of supported particles, the degree of reducibility of cations, etc., in a variety of ways. Our objective is to characterize the physical chemistry of the active phase-oxide support interaction by spectroscopic methods and to correlate this structure with catalytic function. Two catalytic systems and their associated techniques (x-ray absorption and NMR) are discussed in this progress report. Firstly, the interaction of Pt-Ni supported on silica and L-zeolite are characterized and compared by x-ray absorption spectroscopy (EXAFS). Secondly, we present both experimental and calculational developments of NMR for the investigation of amorphous silica-alumina catalysts and/or supports.

  18. Non-Destructive and Discriminating Identification of Illegal Drugs by Transient Absorption Spectroscopy in the Visible and Near-IR Wavelength Range

    NASA Astrophysics Data System (ADS)

    Sato, Chie; Furube, Akihiro; Katoh, Ryuzi; Nonaka, Hidehiko; Inoue, Hiroyuki

    2008-11-01

    We have tested the possibility of identifying illegal drugs by means of nanosecond transient absorption spectroscopy with a 10-ns UV-laser pulse for the excitation light and visible-to-near-IR light for the probe light. We measured the transient absorption spectra of acetonitrile solutions of d-methamphetamine, dl-3,4-methylenedioxymethamphetamine hydrochloride (MDMA), and dl-N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine hydrochloride (MBDB), which are illegal drugs widely consumed in Japan. Transient absorption signals of these drugs were observed between 400 and 950 nm, a range in which they are transparent in the ground state. By analyzing the spectra in terms of exponential and Gaussian functions, we could identify the drugs and discriminate them from chemical substances having similar structures. We propose that transient absorption spectroscopy will be a useful, non-destructive method of inspecting for illegal drugs, especially when they are dissolved in liquids. Such a method may even be used for drugs packed in opaque materials if it is further extended to utilize intense femtosecond laser pulses.

  19. Visualizing Infrared (IR) Spectroscopy with Computer Animation

    NASA Technical Reports Server (NTRS)

    Abrams, Charles B.; Fine, Leonard W.

    1996-01-01

    IR Tutor, an interactive, animated infrared (IR) spectroscopy tutorial has been developed for Macintosh and IBM-compatible computers. Using unique color animation, complicated vibrational modes can be introduced to beginning students. Rules governing the appearance of IR absorption bands become obvious because the vibrational modes can be visualized. Each peak in the IR spectrum is highlighted, and the animation of the corresponding normal mode can be shown. Students can study each spectrum stepwise, or click on any individual peak to see its assignment. Important regions of each spectrum can be expanded and spectra can be overlaid for comparison. An introduction to the theory of IR spectroscopy is included, making the program a complete instructional package. Our own success in using this software for teaching and research in both academic and industrial environments will be described. IR Tutor consists of three sections: (1) The 'Introduction' is a review of basic principles of spectroscopy. (2) 'Theory' begins with the classical model of a simple diatomic molecule and is expanded to include larger molecules by introducing normal modes and group frequencies. (3) 'Interpretation' is the heart of the tutorial. Thirteen IR spectra are analyzed in detail, covering the most important functional groups. This section features color animation of each normal mode, full interactivity, overlay of related spectra, and expansion of important regions. This section can also be used as a reference.

  20. ATR-IR spectroscopy as applied to nucleic acid films

    NASA Astrophysics Data System (ADS)

    Stepanyugin, Andriy V.; Samijlenko, Svitlana P.; Martynenko, Olena I.; Hovorun, Dmytro M.

    2005-07-01

    For the first time the ATR technique was applied to obtain IR absorption spectra of DNA and RNA dry films. There was worked out procedure of the nucleic acid removal from germanium plate, which obviously was a main obstacle to application of ATR-IR spectroscopy to nucleic acids. This technique of IR spectroscopy was applied to confirmation of RNA tropism of aurin tricarboxylic acid observed by molecular biological methods.

  1. IR absorption and reflectometric interference spectroscopy (RIfS) combined to a new sensing approach for gas analytes absorbed into thin polymer films.

    PubMed

    Leopold, Nicolae; Busche, Stefan; Gauglitz, Günter; Lendl, Bernhard

    2009-06-01

    Hydrophobic polymer layers (3 microm) were spin-coated on Si or Ge plates and placed in a flow through gas chamber. FTIR reflection spectra of the layers were recorded showing the characteristic IR absorption bands of the polymer and the interference pattern generated by layered structure of the polymer film. Upon exposure of the polymer layer to gaseous analytes enrichment in the polymer film occurred. This was evidenced by the appearance of analyte specific absorption particular in the mid-IR part of the spectrum, as well as by a shift in the interference pattern across the whole spectrum. Qualitative information concerning the analyte was accessible in the mid-IR part of the spectrum, whereas quantitative assessment was obtained from the interference pattern. Polyetherurethane, polydimethylsiloxane, Makrolon and polyisobutylene polymer layers were tested for such IR-RIfS measurements, whereas toluene, o-dichlorobenzene, m-xylene, ethyl acetate and cyclohexane were employed as analytes. There was no influence of water vapour neither on the IR absorptions nor the interference pattern as hydrophobic polymers were used. PMID:19233714

  2. IR absorption and reflectometric interference spectroscopy (RIfS) combined to a new sensing approach for gas analytes absorbed into thin polymer films

    NASA Astrophysics Data System (ADS)

    Leopold, Nicolae; Busche, Stefan; Gauglitz, Günter; Lendl, Bernhard

    2009-06-01

    Hydrophobic polymer layers (3 μm) were spin-coated on Si or Ge plates and placed in a flow through gas chamber. FTIR reflection spectra of the layers were recorded showing the characteristic IR absorption bands of the polymer and the interference pattern generated by layered structure of the polymer film. Upon exposure of the polymer layer to gaseous analytes enrichment in the polymer film occurred. This was evidenced by the appearance of analyte specific absorption particular in the mid-IR part of the spectrum, as well as by a shift in the interference pattern across the whole spectrum. Qualitative information concerning the analyte was accessible in the mid-IR part of the spectrum, whereas quantitative assessment was obtained from the interference pattern. Polyetherurethane, polydimethylsiloxane, Makrolon ® and polyisobutylene polymer layers were tested for such IR-RIfS measurements, whereas toluene, o-dichlorobenzene, m-xylene, ethyl acetate and cyclohexane were employed as analytes. There was no influence of water vapour neither on the IR absorptions nor the interference pattern as hydrophobic polymers were used.

  3. Relic Neutrino Absorption Spectroscopy

    SciTech Connect

    Eberle, b

    2004-01-28

    Resonant annihilation of extremely high-energy cosmic neutrinos on big-bang relic anti-neutrinos (and vice versa) into Z-bosons leads to sizable absorption dips in the neutrino flux to be observed at Earth. The high-energy edges of these dips are fixed, via the resonance energies, by the neutrino masses alone. Their depths are determined by the cosmic neutrino background density, by the cosmological parameters determining the expansion rate of the universe, and by the large redshift history of the cosmic neutrino sources. We investigate the possibility of determining the existence of the cosmic neutrino background within the next decade from a measurement of these absorption dips in the neutrino flux. As a by-product, we study the prospects to infer the absolute neutrino mass scale. We find that, with the presently planned neutrino detectors (ANITA, Auger, EUSO, OWL, RICE, and SalSA) operating in the relevant energy regime above 10{sup 21} eV, relic neutrino absorption spectroscopy becomes a realistic possibility. It requires, however, the existence of extremely powerful neutrino sources, which should be opaque to nucleons and high-energy photons to evade present constraints. Furthermore, the neutrino mass spectrum must be quasi-degenerate to optimize the dip, which implies m{sub {nu}} 0.1 eV for the lightest neutrino. With a second generation of neutrino detectors, these demanding requirements can be relaxed considerably.

  4. X-ray Absorption Spectroscopy

    SciTech Connect

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

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

  5. An investigation of catalytic active phase-support interactions by IR, NMR and x-ray absorption spectroscopies. Progress report, January 15, 1992--September 15, 1992

    SciTech Connect

    Haller, G.L.

    1992-09-01

    Active catalytic phases (metal, mixed metals, oxide or mixed oxides) interacting with oxide support on which the active phase is dispersed can affect the percentage exposed, the morphology of supported particles, the degree of reducibility of cations, etc., in a variety of ways. Our objective is to characterize the physical chemistry of the active phase-oxide support interaction by spectroscopic methods and to correlate this structure with catalytic function. Two catalytic systems and their associated techniques (x-ray absorption and NMR) are discussed in this progress report. Firstly, the interaction of Pt-Ni supported on silica and L-zeolite are characterized and compared by x-ray absorption spectroscopy (EXAFS). Secondly, we present both experimental and calculational developments of NMR for the investigation of amorphous silica-alumina catalysts and/or supports.

  6. Cavity Enhanced Ultrafast Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Allison, Thomas K.; Reber, Melanie Roberts; Chen, Yuning

    2015-06-01

    Ultrafast spectroscopy on gas phase systems is typically restricted to techniques involving photoionization, whereas solution phase experiments utilize the detection of light. At Stony Brook, we are developing new techniques for performing femtosecond time-resolved spectroscopy using frequency combs and high-finesse optical resonators. A large detection sensitivity enhancement over traditional methods enables the extension of all-optical ultrafast spectroscopies, such as broad-band transient absorption spectroscopy (TAS) and 2D spectroscopy, to dilute gas phase samples produced in molecular beams. Here, gas phase data can be directly compared to solution phase data. Initial demonstration experiments are focusing on the photodissociation of iodine in small neutral argon clusters, where cluster size strongly influences the effects solvent-caging and geminate recombination. I will discuss these initial results, our high power home-built Yb:fiber laser systems, and also extensions of the methods to the mid-IR to study the vibrational dynamics of hydrogen bonded clusters.

  7. Cavity-Enhanced Ultrafast Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Yuning; Reber, Melanie Roberts; Keleher, Kevin; Allison, Thomas K.

    2014-06-01

    We introduce cavity enhanced ultrafast transient absorption spectroscopy, which employs frequency combs and high-finesse optical cavities. % The schematic of apparatus is shown in Figure 1. Sub-100 fs pulses with a repetition rate of 90 MHz are generated by a home-built Ytterbium fiber laser. The amplified light has a power up to 10 W, which is used to pump an optical parametric oscillator, followed by second-harmonic generation(SHG) that converts the wavelength from near-IR to visible. A pump comb at 530 nm is separately generated by SHG. Both pump and probe combs are coupled into high-finesse cavities. Compared to the conventional transient absorption spectroscopy method, the detection sensitivity can be improved by a factor of (F/π)^2 ˜ 10^5, where F is the finesse of cavity. This ultrasensitive technology enables the direct all-optical dynamics study in molecular beams. We will apply the cavity enhanced ultrafast transient absorption spectroscopy to investigate the dynamics of visible chromophores and then extend the wavelength to mid-IR to study vibrational dynamics of small hydrogen-bonded clusters.

  8. NEW ACCURATE MEASUREMENT OF {sup 36}ArH{sup +} AND {sup 38}ArH{sup +} RO-VIBRATIONAL TRANSITIONS BY HIGH RESOLUTION IR ABSORPTION SPECTROSCOPY

    SciTech Connect

    Cueto, M.; Herrero, V. J.; Tanarro, I.; Doménech, J. L.; Cernicharo, J.; Barlow, M. J.; Swinyard, B. M.

    2014-03-01

    The protonated argon ion, {sup 36}ArH{sup +}, was recently identified in the Crab Nebula from Herschel spectra. Given the atmospheric opacity at the frequency of its J = 1-0 and J = 2-1 rotational transitions (617.5 and 1234.6 GHz, respectively), and the current lack of appropriate space observatories after the recent end of the Herschel mission, future studies on this molecule will rely on mid-infrared observations. We report on accurate wavenumber measurements of {sup 36}ArH{sup +} and {sup 38}ArH{sup +} rotation-vibration transitions in the v = 1-0 band in the range 4.1-3.7 μm (2450-2715 cm{sup –1}). The wavenumbers of the R(0) transitions of the v = 1-0 band are 2612.50135 ± 0.00033 and 2610.70177 ± 0.00042 cm{sup –1} (±3σ) for {sup 36}ArH{sup +} and {sup 38}ArH{sup +}, respectively. The calculated opacity for a gas thermalized at a temperature of 100 K and with a linewidth of 1 km s{sup –1} of the R(0) line is 1.6 × 10{sup –15} × N({sup 36}ArH{sup +}). For column densities of {sup 36}ArH{sup +} larger than 1 × 10{sup 13} cm{sup –2}, significant absorption by the R(0) line can be expected against bright mid-IR sources.

  9. Time-Resolved Quantitative Measurement of OH HO2 and CH2O in Fuel Oxidation Reactions by High Resolution IR Absorption Spectroscopy.

    SciTech Connect

    Huang, Haifeng; Rotavera, Brandon; Taatjes, Craig A.

    2014-08-01

    Combined with a Herriott-type multi-pass slow flow reactor, high-resolution differential direct absorption spectroscopy has been used to probe, in situ and quantitatively, hydroxyl (OH), hydroperoxy (HO 2 ) and formaldehyde (CH 2 O) molecules in fuel oxidation reactions in the reactor, with a time resolution of about 1 micro-second. While OH and CH 2 O are probed in the mid-infrared (MIR) region near 2870nm and 3574nm respectively, HO 2 can be probed in both regions: near-infrared (NIR) at 1509nm and MIR at 2870nm. Typical sensitivities are on the order of 10 10 - 10 11 molecule cm -3 for OH at 2870nm, 10 11 molecule cm -3 for HO 2 at 1509nm, and 10 11 molecule cm -3 for CH 2 O at 3574nm. Measurements of multiple important intermediates (OH and HO 2 ) and product (CH 2 O) facilitate to understand and further validate chemical mechanisms of fuel oxidation chemistry.

  10. An investigation of catalytic active phase-support interactions by IR, NMR and x-ray absorption spectroscopies. Progress report, January 15, 1991--July 31, 1993

    SciTech Connect

    Haller, G.L.

    1993-07-01

    Active catalytic phases (metal, mixed metals, oxide or mixed oxides) interacting with oxide support can affect percentage exposed, the morphology of supported particles, the degree of reducibility of cations, etc., in a variety of ways. Solid state {sup 29}Si NMR was used to obtain a new correlation between partial charge on the Si which comprises a part of the SiOHAl Br{o}nsted acid structure in amorphous silica-aluminas. We also describe two potential improvements in solid state NMR applied to catalysts and catalysts supports. One is experimental, dynamic angle spinning NMR, a new technique for obtaining high resolution spectra of quadrupolar nuclei, e.g., {sup 27}Al. The second approach is an alternative to the standard fast Fourier transform of the free induction decay to convert from the time to spectral domain, the maximum entropy method. Effect of different methods of preparation of Pd/L-zeolites is described. By comparison to analogous Pt systems, it is the inherent chemistry of the L-zeolite which results in better dispersion when impregnation preparation is used relative to ion exchange preparation. X-ray absorption spectroscopy is used to compare the effect of support (SiO{sub 2} and L-zeolite) on the degree and kind of Pt-Ni interaction. When supported in L-zeolite and promoted with Ni, Pt has improved stability both with regard to self-poisoning and sulfur catalyzed agglomeration.

  11. The atomic structural dynamics of γ-Al2O3 supported Ir-Pt nanocluster catalysts prepared from a bimetallic molecular precursor: a study using aberration-corrected electron microscopy and X-ray absorption spectroscopy.

    PubMed

    Small, Matthew W; Sanchez, Sergio I; Menard, Laurent D; Kang, Joo H; Frenkel, Anatoly I; Nuzzo, Ralph G

    2011-03-16

    This study describes a prototypical, bimetallic heterogeneous catalyst: compositionally well-defined Ir-Pt nanoclusters with sizes in the range of 1-2 nm supported on γ-Al(2)O(3). Deposition of the molecular bimetallic cluster [Ir(3)Pt(3)(μ-CO)(3)(CO)(3)(η-C(5)Me(5))(3)] on γ-Al(2)O(3), and its subsequent reduction with hydrogen, provides highly dispersed supported bimetallic Ir-Pt nanoparticles. Using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM) and theoretical modeling of synchrotron-based X-ray absorption spectroscopy (XAS) measurements, our studies provide unambiguous structural assignments for this model catalytic system. The atomic resolution C(s)-STEM images reveal strong and specific lattice-directed strains in the clusters that follow local bonding configurations of the γ-Al(2)O(3) support. Combined nanobeam diffraction (NBD) and high-resolution transmission electron microscopy (HRTEM) data suggest the polycrystalline γ-Al(2)O(3) support material predominantly exposes (001) and (011) surface planes (ones commensurate with the zone axis orientations frequently exhibited by the bimetallic clusters). The data reveal that the supported bimetallic clusters exhibit complex patterns of structural dynamics, ones evidencing perturbations of an underlying oblate/hemispherical cuboctahedral cluster-core geometry with cores that are enriched in Ir (a result consistent with models based on surface energetics, which favor an ambient cluster termination by Pt) due to the dynamical responses of the M-M bonding to the specifics of the adsorbate and metal-support interactions. Taken together, the data demonstrate that strong temperature-dependent charge-transfer effects occur that are likely mediated variably by the cluster-support, cluster-adsorbate, and intermetallic bonding interactions. PMID:21341654

  12. Methane overtone absorption by intracavity laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Obrien, James J.

    1990-01-01

    Interpretation of planetary methane (CH4) visible-near IR spectra, used to develop models of planetary atmospheres, has been hampered by a lack of suitable laboratory spectroscopic data. The particular CH4 spectral bands are due to intrinsically weak, high overtone-combination transitions too complex for classical spectroscopic analysis. The traditional multipass cell approach to measuring spectra of weakly absorbing species is insufficiently sensitive to yield reliable results for some of the weakest CH4 absorption features and is difficult to apply at the temperatures of the planetary environments. A time modulated form of intracavity laser spectroscopy (ILS), has been shown to provide effective absorption pathlengths of 100 to 200 km with sample cells less than 1 m long. The optical physics governing this technique and the experimental parameters important for obtaining reliable, quantitative results are now well understood. Quantitative data for CH4 absorption obtained by ILS have been reported recently. Illustrative ILS data for CH4 absorption in the 619.7 nm and 681.9 nm bands are presented. New ILS facilities at UM-St. Louis will be used to measure CH4 absorption in the 700 to 1000 nm region under conditions appropriate to the planetary atmospheres.

  13. IR Spectroscopy and Photo-Chemistry of Extraterrestrial Ices

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Mastrapa, Rachel; Elsila, Jamie; Sandford, Scott

    2005-01-01

    Dense molecular clouds from which planetary systems form and the outer Solar System are both cold environments dominated by ices. Infrared (IR) spectroscopy is used to probe these ices, but the IR absorptions of molecules depend on the conditions. As a result appropriate lab data is needed to correctly fit spectra of extraterrestrial ices. Such fits have shown that most of these ices are composed primarily of H2O, but also contain 1-10 percent of other simple molecules such as CO2, CO, CH4, & NH3;. We shall present near IR spectra of ice mixtures of relevance to icy outer Solar System bodies and show that they still hold surprises, such as the Cheshire cat-like CO2 (2v3) overtone near 2.134 micrometers (4685 cm-1) that is absent from spectra of pure CO2 but present in H2O-CO2 mixtures.

  14. Cross-polarized optical absorption of single-walled carbon nanotubes probed by photoluminescence excitation spectroscopy, UV-Vis-IR and polarized Raman Scatterings

    NASA Astrophysics Data System (ADS)

    Maruyama, Shigeo

    2008-03-01

    Because of the depolarization effect, or so-called antenna effect, optical absorption of single-walled carbon nanotubes (SWNTs) is weak when excited by light polarized perpendicular to the nanotube axis. However, in photoluminescence (PL) excitation spectra of isolated SWNTs, PL peaks due to cross-polarized excitation can be clearly identified. By decomposing the cross-polarized component, the optical transition energy of E12 or E21 can be? measured, and the smaller exciton binding energy for perpendicular excitations is concluded [1]. Cross-polarized absorption is dominant in the absorption of a vertically aligned film of SWNTs [2] when excited from the top of the film. In our previous study, a pi-plasmon absorption at 5.25 eV was revealed in contrast to 4.5 eV for parallel excitation [3]. Resonant Raman scattering from such a film is also influenced by the cross-polarized excitation [4]. Even though a Kataura plot for the E33 and E44 range has been proposed by using such a vertically aligned film [5], polarized Raman scattering spectra reveal more complicated features in the system because of the small bundle size, typically 5-8 nanotubes [6]. References: [1] Y. Miyauchi, M. Oba, S. Maruyama, Phys. Rev. B 74 (2006) 205440. [2] Y. Murakami, S. Chiashi, Y. Miyauchi, M. Hu, M. Ogura, T. Okubo, S. Maruyama, Chem. Phys. Lett. 385 (2004) 298. [3] Y. Murakami, E. Einarsson, T. Edamura, S. Maruyama, Phys. Rev. Lett. 94 (2005) 087402. [4] Y. Murakami, S. Chiashi, E. Einarsson, S. Maruyama, Phys. Rev. B 71 (2005) 085403. [5] P. T. Araujo, S. K. Doorn, S. Kilina, S. Tretiak, E. Einarsson, S. Maruyama, H. Chacham, M. A. Pimenta, A. Jorio, Phys. Rev. Lett. 88 (2007) 067401. [6] E. Einarsson, H. Shiozawa, C. Kramberger, M. H. Ruemmeli, A. Gruneis, T. Pichler, S. Maruyama, J. Phys. Chem. C (2007) published on Web.

  15. Absorption Spectroscopy in Homogeneous and Micellar Solutions.

    ERIC Educational Resources Information Center

    Shah, S. Sadiq; Henscheid, Leonard G.

    1983-01-01

    Describes an experiment which has helped physical chemistry students learn principles of absorption spectroscopy, the effect of solvent polarity on absorption spectra, and some micellar chemistry. Background information and experimental procedures are provided. (JN)

  16. Graphene intracavity spaser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lozovik, Yu. E.; Nechepurenko, I. A.; Dorofeenko, A. V.

    2016-09-01

    We propose an intracavity plasmon absorption spectroscopy method based on graphene active plasmonics. It is shown that the plasmonic cavity contribution to the sensitivity is proportional to the quality factor Q of the graphene plasmonic cavity and reaches two orders of magnitude. The addition of gain medium into the cavity increases the sensitivity of method. Maximum sensitivity is reached in the vicinity of the plasmon generation threshold. The gain contribution to the sensitivity is proportional to Q1/2. The giant amplification of sensitivity in the graphene plasmon generator is associated with a huge path length, limited only by the decoherence processes. An analytical estimation of the sensitivity to loss caused by analyzed particles (molecules, nanoparticles, etc.) normalized by the single pass plasmon scheme is derived. Usage of graphene nanoflakes as plasmonic cavity allows a high spatial resolution to be reached, in addition to high sensitivity.

  17. IR Cards: Inquiry-Based Introduction to Infrared Spectroscopy

    ERIC Educational Resources Information Center

    Bennett, Jacqueline; Forster, Tabetha

    2010-01-01

    As infrared spectroscopy (IR) is frequently used in undergraduate organic chemistry courses, an inductive introduction to IR spectroscopy that uses index cards printed with spectra, structures, and chemical names is described. Groups of students are given an alphabetized deck of these "IR cards" to sort into functional groups. The students then…

  18. IR absorption spectra of cellulose obtained from ozonated wood

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  19. Fingerprints of polycyclic aromatic hydrocarbons (PAHs) in infrared absorption spectroscopy.

    PubMed

    Tommasini, Matteo; Lucotti, Andrea; Alfè, Michela; Ciajolo, Anna; Zerbi, Giuseppe

    2016-01-01

    We have analyzed a set of 51 PAHs whose structures have been hypothesized from mass spectrometry data collected on samples extracted from carbon particles of combustion origin. We have obtained relationships between infrared absorption signals in the fingerprint region (mid-IR) and the chemical structures of PAHs, thus proving the potential of IR spectroscopy for the characterization of the molecular structure of aromatic combustion products. The results obtained here for the spectroscopic characterization of PAHs can be also of interest in Materials Science and Astrophysics. PMID:26208268

  20. Fingerprints of polycyclic aromatic hydrocarbons (PAHs) in infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tommasini, Matteo; Lucotti, Andrea; Alfè, Michela; Ciajolo, Anna; Zerbi, Giuseppe

    2016-01-01

    We have analyzed a set of 51 PAHs whose structures have been hypothesized from mass spectrometry data collected on samples extracted from carbon particles of combustion origin. We have obtained relationships between infrared absorption signals in the fingerprint region (mid-IR) and the chemical structures of PAHs, thus proving the potential of IR spectroscopy for the characterization of the molecular structure of aromatic combustion products. The results obtained here for the spectroscopic characterization of PAHs can be also of interest in Materials Science and Astrophysics.

  1. Estimation of molar absorptivities and pigment sizes for eumelanin and pheomelanin using femtosecond transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Piletic, Ivan R.; Matthews, Thomas E.; Warren, Warren S.

    2009-11-01

    Fundamental optical and structural properties of melanins are not well understood due to their poor solubility characteristics and the chemical disorder present during biomolecular synthesis. We apply nonlinear transient absorption spectroscopy to quantify molar absorptivities for eumelanin and pheomelanin and thereby get an estimate for their average pigment sizes. We determine that pheomelanin exhibits a larger molar absorptivity at near IR wavelengths (750nm), which may be extended to shorter wavelengths. Using the molar absorptivities, we estimate that melanin pigments contain ˜46 and 28 monomer units for eumelanin and pheomelanin, respectively. This is considerably larger than the oligomeric species that have been recently proposed to account for the absorption spectrum of eumelanin and illustrates that larger pigments comprise a significant fraction of the pigment distribution.

  2. A novel CO 2 gas analyzer based on IR absorption

    NASA Astrophysics Data System (ADS)

    Zhang, Guangjun; Wu, Xiaoli

    2004-08-01

    Carbon dioxide (CO 2) gas analyzer can be widely used in many fields. A novel CO 2 gas analyzer based on infrared ray (IR) absorption is presented sufficiently in this paper. Applying Lambert-Beer Law, a novel space-double-beam optical structure is established successfully. The optical structure includes an IR source, a gas cell, a bandpass filter with a transmission wavelength at 4.26 μm, another bandpass filter with a transmission wavelength at 3.9 μm, and two IR detectors. Based on Redial Basic Function (RBF) artificial neural network, the measuring model of IR CO 2 analyzer is established with a high accuracy. A dynamic compensation filter is effectively designed to improve the dynamic characteristic of the IR CO 2 analyzer without gas pump. The IR CO 2 analyzer possesses the advantages of high accuracy and mechanical reliability with small volume, lightweight, and low-power consumption. Therefore, it can be used in such relevant fields as environmental protection, processing control, chemical analysis, medical diagnosis, and space environmental and control systems.

  3. Absorption intensity changes and frequency shifts of fundamental and first overtone bands for OH stretching vibration of methanol upon methanol-pyridine complex formation in CCl4: analysis by NIR/IR spectroscopy and DFT calculations.

    PubMed

    Futami, Yoshisuke; Ozaki, Yasushi; Ozaki, Yukihiro

    2016-02-21

    Infrared (IR) and near infrared (NIR) spectra were measured for methanol and the methanol-pyridine complex in carbon tetrachloride. Upon the formation of the methanol-pyridine complex, the frequencies of both the fundamental and first overtone bands of the OH stretching vibration shifted to lower frequencies, and the absorption intensity of the fundamental increased significantly, while that of the first overtone decreased markedly. By using quantum chemical calculations, we estimated the absorption intensities and frequencies of the fundamental and first overtone bands for the OH stretching vibration based on the one-dimensional Schrödinger equation. The calculated results well reproduced the experimental results. The molecular vibration potentials and dipole moment functions of the OH stretching vibration modes were compared between methanol and the methanol-pyridine complex in terms of absorption intensity changes and frequency shifts. The large change in the dipole moment function was found to be the main cause for the variations in absorption intensity for the fundamental and first overtone bands. PMID:26862859

  4. Neuron absorption study and mid-IR optical excitations

    NASA Astrophysics Data System (ADS)

    Guo, Dingkai; Chen, Xing; Vadala, Shilpa; Leach, Jennie; Kostov, Yordan; Bewley, William W.; Kim, Chul-Soo; Kim, Mijin; Canedy, Chadwick L.; Merritt, Charles D.; Vurgaftman, Igor; Meyer, Jerry R.; Choa, Fow-Sen

    2012-02-01

    Neuronal optical excitation can provide non-contacting tools to explore brain circuitry and a durable stimulation interface for cardiac pacing and visual as well as auditory sensory neuronal stimulation. To obtain accurate absorption spectra, we scan the transmission of neurons in cell culture medium, and normalize it by subtracting out the absorption spectrum of the medium alone. The resulting spectra show that the main neuronal absorption peaks are in the 3000- 6000nm band, although there is a smaller peak near 1450nm. By coupling the output of a 3μm interband cascade laser (ICL) into a mid-IR fluorozirconate fiber, we can effectively deliver more than 1J/cm2 photon intensity to the excitation site for neuronal stimulation.

  5. Further advancement of differential optical absorption spectroscopy: theory of orthogonal optical absorption spectroscopy.

    PubMed

    Liudchik, Alexander M

    2014-08-10

    A modified version of the differential optical absorption spectroscopy (DOAS) method is presented. The technique is called orthogonal optical absorption spectroscopy (OOAS). A widespread variant of DOAS with smoothing of the registered spectrum and absorption cross sections being made employing a polynomial regression is a particular case of OOAS. The concept of OOAS provides a variety of new possibilities for constructing computational schemes and analyzing the influence of different error sources on calculated concentrations. PMID:25320931

  6. Infrared spectroscopy of radio-luminous OH/IR stars

    NASA Technical Reports Server (NTRS)

    Jones, Terry Jay; Hyland, A. R.; Fix, John D.; Cobb, Michael L.

    1988-01-01

    Low-resolution 1.5-2.5-micron spectra for 21 radio-luminous OH/IR stars are presented. These spectra divide into two broad classes. Those with very strong water-vapor absorption closely resemble the spectra of classical Mira variables and are classified Type VM. Those with weaker water-vapor absorption, but still showing strong CO absorption, resemble the spectra of true core-burning supergiants and are classified Type SG. Comparison of the classification of 30 radio-luminous OH/IR stars with their Delta(V)s and luminosities suggests this classification is a good indicator of the intrinsic nature of the underlying star. There is some evidence, however, that some true supergiants (massive main-sequence progenitors) develop the pulsation properties and photospheric characteristics of the Mira-like OH/IR stars when they become optically obscured OH/IR stars.

  7. Preliminary study of corrosion mechanisms of actinides alloys: calibration of FT-IR spectroscopy

    SciTech Connect

    Magnien, Veronique; Cadignan, Marx; Faivret, Olivier; Rosa, Gaelle

    2008-07-01

    In situ analyzes of gaseous atmospheres could be performed by FT-IR spectroscopy in order to study the corrosion reactions of actinides. Nevertheless experimental conditions and the nature of studied species have a strong effect on IR absorption laws. Thus a prior calibration of our set-up is required to obtain an accurate estimation of gas concentration. For this purpose, the behavior of several air pure gases has been investigated according to their concentration from IR spectra. Reproducible results revealed subsequent increases of the most significant peak areas with gas pressure and small deviations from Beer Lambert's law. This preliminary work allowed to determine precise absorption laws for each studied pure gas in our in situ experimental conditions. Besides our FT-IR set-up was well suitable to quantitative analysis of gaseous atmosphere during corrosion reactions. Finally the effect of foreign gas will be investigated through more complex air mixtures to obtain a complete calibration network. (authors)

  8. Exploiting the IR: Solar and stellar spectroscopy in the IR

    NASA Technical Reports Server (NTRS)

    Deming, Drake

    1987-01-01

    Recent instrumental advances have provided the capability to perform high resolution spectroscopy, in the thermal infrared region of the solar spectrum, with high sensitivity. The 8 to 12 micron region was extensively observed using Fourier transform (FTS) and laser heterodyne techniques. The continuous opacity of the solar atmosphere, due to H(-), increases with wavelength in the infrared region longward of 1.6 microns. Consequently thermal infrared observations probe the upper photosphere, and give an insight into the dynamics and structure of this region. The most notable spectral features in the 10 micron window include pure rotation lines of OH, and emission lines due to high-n states in MgI and AlI. The high-n lines due to MgI and AlI are important to solar and stellar physics because of their very large Zeeman sensitivity. The recent development of a cryogenic grating postdispenser for the FTS has allowed low-noise solar observations of these lines in 90 seconds. Limited mapping of the lines in a sunspot penumbra was performed, and gives information of the structure of the penumbral magnetic field. Although the MgI lines were detected in red giant spectra, instrumental sensitivity is not yet sufficient to see them in stars where significant magnetic fields are expected.

  9. Polaronic absorption in Sr2IrO4

    NASA Astrophysics Data System (ADS)

    Sohn, Chang Hee; Qi, Tong-Fei; Noh, Kyung Joo; Park, Hyun-Ju; Yoo, Hyang Keun; Cao, Gang; Kim, Kyung Wan; Cho, Deok-Yong; Moon, Soon Jae; Noh, Tae Won

    2014-03-01

    Sr2IrO4 has received much attention as a novel Jeff = 1/2 Mott insulator. Many theorists have supposed that exotic novel ground state such as superconductivity, topological insulator, and quantum spin liquid could emerge in Jeff = 1/2 state. However, despite of great interests on Sr2IrO4, the ground state of this material is elusive up to now. Unlike previous Mott scenario, recent reports support that Sr2IrO4 can be described as Slater insulator rather than Mott insulator. The origin of temperature evolutions of electronic structure shown in many experiments also remains vague until now. Here, we investigated the detail temperature evolution of electronic structure of Sr2IrO4 using infrared spectroscopy. We couldn't observe any anomaly in optical conductivity near the TN, which is not consistent with recent reports. Instead, we observed the continuous changes in our optical data which can be explained in terms of polaronic behavior, closely related to La2CuO4.

  10. Transient 2D IR spectroscopy of charge injection in dye-sensitized nanocrystalline thin films.

    PubMed

    Xiong, Wei; Laaser, Jennifer E; Paoprasert, Peerasak; Franking, Ryan A; Hamers, Robert J; Gopalan, Padma; Zanni, Martin T

    2009-12-23

    We use nonlinear 2D IR spectroscopy to study TiO(2) nanocrystalline thin films sensitized with a Re dye. We find that the free electron signal, which often obscures the vibrational features in the transient absorption spectrum, is not observed in the 2D IR spectra. Its absence allows the vibrational features of the dye to be much better resolved than with the typical IR absorption probe. We observe multiple absorption bands but no cross peaks in the 2D IR spectra, which indicates that the dyes have at least three conformations. Furthermore, by using a pulse sequence in which we initiate electron transfer in the middle of the infrared pulse train, we are able to assign the excited state features by correlating them to the ground state vibrational modes and determine that the three conformations have different time scales and cross sections for electron injection. 2D IR spectroscopy is proving to be very useful in disentangling overlapping structural distributions in biological and chemical physics processes. These experiments demonstrate that nonlinear infrared probes are also a powerful new tool for studying charge transfer at interfaces. PMID:19947603

  11. Simultaneous multi-beam planar array IR (pair) spectroscopy

    DOEpatents

    Elmore, Douglas L.; Rabolt, John F.; Tsao, Mei-Wei

    2005-09-13

    An apparatus and method capable of providing spatially multiplexed IR spectral information simultaneously in real-time for multiple samples or multiple spatial areas of one sample using IR absorption phenomena requires no moving parts or Fourier Transform during operation, and self-compensates for background spectra and degradation of component performance over time. IR spectral information and chemical analysis of the samples is determined by using one or more IR sources, sampling accessories for positioning the samples, optically dispersive elements, a focal plane array (FPA) arranged to detect the dispersed light beams, and a processor and display to control the FPA, and display an IR spectrograph. Fiber-optic coupling can be used to allow remote sensing. Portability, reliability, and ruggedness is enhanced due to the no-moving part construction. Applications include determining time-resolved orientation and characteristics of materials, including polymer monolayers. Orthogonal polarizers may be used to determine certain material characteristics.

  12. Standoff imaging of chemicals using IR spectroscopy

    SciTech Connect

    Senesac, Larry R; Thundat, Thomas George; Morales Rodriguez, Marissa E

    2011-01-01

    Here we report on a standoff spectroscopic technique for identifying chemical residues on surfaces. A hand-held infrared camera was used in conjunction with a wavelength tunable mid-IR quantum cascade laser (QCL) to create hyperspectral image arrays of a target with an explosive residue on its surface. Spectral signatures of the explosive residue (RDX) were extracted from the hyperspectral image arrays and compared with a reference spectrum. Identification of RDX was achieved for residue concentrations of 20 g per cm2 at a distance of 1.5 m, and for 5 g per cm2 at a distance of 15 cm.

  13. Ir Spectroscopy and Nickel (II) Hexammines

    ERIC Educational Resources Information Center

    Reedijk, J.; And Others

    1975-01-01

    Describes an experiment, for the general chemistry laboratory, intended to introduce the student to infrared spectroscopy. After being introduced to the theory of molecular vibrations on an elementary level, each student receives a list of 5-7 nickel (II) ammines to be prepared, analyzed and characterized by infrared spectoscopy. (MLH)

  14. Absorption spectroscopy with quantum cascade lasers

    NASA Technical Reports Server (NTRS)

    Kosterev, A. A.; Curl, R. F.; Tittel, F. K.; Gmachl, C.; Capasso, F.; Sivco, D. L.; Baillargeon, J. N.; Hutchinson, A. L.; Cho, A. Y.

    2001-01-01

    Novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers operating near lambda=8 micrometers were used for detection and quantification of trace gases in ambient air by means of sensitive absorption spectroscopy. N2O, 12CH4, 13CH4, and different isotopic species of H2O were detected. Also, a highly selective detection of ethanol vapor in air with a sensitivity of 125 parts per billion by volume (ppb) was demonstrated.

  15. Phase Fluctuation Absorption Spectroscopy of Small Particles

    NASA Astrophysics Data System (ADS)

    Fluckiger, David Ulrich

    The purpose of this dissertation is to establish a viable mass measurement technique for in situ aerosol. Adaptation of the photothermal effect in a Mach-Zehnder interferometer provided high mass sensitivity in an instrument employing Phase Fluctuation Laser Optical Heterodyne (PFLOH) absorption spectroscopy. The theory of aerosol absorption of electromagnetic energy and subsequent thermalization in continuum, Rayleigh regime region is presented. From this theory the general behavior of PFLOH detection of aerosol is described and shown to give a signal proportional to the absorption species mass. Furthermore the signal is shown to be linear in excitation energy and modulation frequency, and scalable. The instrument is calibrated and shown to behave as predicted. PFLOH detection is then used in determining the mass size distribution of the aerosol component of the ozone-isoprene and ozone -(alpha)-pinene products as a function of isoprene and (alpha) -pinene concentration.

  16. CO2 Absorption Spectroscopy and Climate Change

    NASA Astrophysics Data System (ADS)

    Feldman, Daniel; Mlawer, Eli; Mlynczak, Martin; Gero, Jon; Collins, William; Torn, Margaret

    2014-03-01

    Most of the absorption, and therefore radiative forcing, due to increased atmospheric CO2 occurs in line wings, so utilizing an accurate line shape is necessary for climate science. Recent advances in CO2 absorption spectroscopy have been incorporated into benchmark line-by-line radiative transfer models. These updates include the Energy Corrected Sudden Approximation to represent isolated line profiles, line mixing, and line clusters. The CO2 line profiles are sub-Lorentzian and are explicitly modeled up to 25 cm-1 from each line's center. Consistent continuum absorption is implemented over the remainder of the profile except for modest empirical adjustments based on observations. Thus, line-by-line models calculate the absorption effects of CO2 that agree with theory and measurements. This is validated with long-term spectroscopic measurements from the ARM program's AERI instrument. This spectroscopy trains computationally-efficient correlated-k methods for climate model radiative transfer, but they overpredict instantaneous radiative forcing from doubled CO2 by approximately 7% in part because they have larger errors handling the impact of increased CO2 in the stratosphere than the troposphere. The implications of this can be tested with supercomputers. This work was supported by the Director, Office of Science, Office of Biol. & Env. Res., Clim. & Env. Sci. Div., of the U.S. D.O.E., Contract No. DE-AC02-05CH11231 as part of the Atmos. Sys. Res.

  17. Remote sensing by IR heterodyne spectroscopy

    NASA Technical Reports Server (NTRS)

    Kostiuk, T.; Mumma, M. J.

    1983-01-01

    The use of infrared heterodyne spectroscopy for the study of planetary atmospheres is discussed. Infrared heterodyne spectroscopy provides a convenient and sensitive method for measuring the true intensity profiles of atmospheric spectral lines. Application of radiative transfer theory to measured lineshapes can then permit the study of molecular abundances, temperatures, total pressures, excitation conditions, and dynamics of the regions of line formation. The theory of formation of atmospheric spectral lines and the retrieval of the information contained in these molecular lines is illustrated. Notable successes of such retrievals from infrared heterodyne measurements on Venus, Mars, Jupiter and the earth are given. A discussion of developments in infrared heterodyne technology is also presented. Previously announced in STAR as N83-28551

  18. New applications of fiber-optic IR spectroscopy in urologic practice

    NASA Astrophysics Data System (ADS)

    Cytron, Shmuel E.; Kravchick, Sergey; Sela, Ben-Ami; Shulzinger, Evgeny; Vasserman, Irena; Raichlin, Yosef; Katzir, Abraham

    2002-03-01

    The objective of this work was to use infrared (IR) fiberoptic spectroscopy for the analysis of urinary salts. Urine samples were obtained (with no sample preparation) from two groups of patients: 24 stone forming patients, after shock wave lithotripsy, and 24 normal subjects of similar ages. IR absorption measurements were performed in real time, using Fiberoptic Evanescent Wave Spectroscopy system, based on IR transmitting silver halide fibers. The absorption data were compared with the IR spectra of aqueous solutions with known concentrations of known urinary salts. The results were then used for the study of the chemical composition of salts in urine samples and for a quantitative analysis of the concentration of these salts. We established the composition of the stones in 20 of the 24 stone forming patients, based on the characteristic absorption peaks for oxalates, carbonates, urates and phosphates observed in their urinary samples. We also determined the concentrations of these salts in the urine samples with average error of 20 percent.

  19. Absorption effects in diffusing wave spectroscopy.

    PubMed

    Sarmiento-Gomez, Erick; Morales-Cruzado, Beatriz; Castillo, Rolando

    2014-07-20

    The effect of absorption in diffusing wave spectroscopy (DWS) was studied using an absorption-dependent diffusive equation for describing the light propagation within a turbid liquid where dielectric microspheres have been embedded. Here, we propose an expression for the time-averaged light intensity autocorrelation function that correctly describes the time fluctuations for the scattered light, in the regime where the diffusion approximation accurately describes the light propagation. This correction was suspected previously, but it was not formally derived from a light diffusive equation. As in the case of no absorption, we obtained that time fluctuations of the scattered light can be related to the mean square displacement of the embedded particles. However, if a correction for absorption is not taken into account, the colloidal dynamics can be misinterpreted. Experimental results show that this new formulation correctly describes the time fluctuations of scattered light. This new procedure extends the applicability of DWS, and it opens the possibility of doing microrheology with this optical method in systems where absorption cannot be avoided. PMID:25090203

  20. OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy.

    PubMed

    Bartula, Renata J; Ghandhi, Jaal B; Sanders, Scott T; Mierkiewicz, Edwin J; Roesler, Fred L; Harlander, John M

    2007-12-20

    We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span approximately 308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of approximately 2x10(-7) m(2) rad(2)) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines. PMID:18091974

  1. OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy

    NASA Astrophysics Data System (ADS)

    Bartula, Renata J.; Ghandhi, Jaal B.; Sanders, Scott T.; Mierkiewicz, Edwin J.; Roesler, Fred L.; Harlander, John M.

    2007-12-01

    We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span ~308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of ~2×10-7 m2 rad2) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines.

  2. Phonon assisted IR spectroscopy of quantum antiferromagnets

    SciTech Connect

    Lorenzana, J.; Eder, R.; Sawatzky, G.A.

    1996-12-31

    The authors review resent theoretical results for multimagnon-phonon assisted infrared absorption in antiferromagnetic Heisenberg systems. They show spin wave theory line shapes for 2D spin 1/2 systems (like the parent insulating high-Tc cuprates) 1D spin 1/2 systems and 2D spin 1 systems (like the nickelates) and exact diagonalization results in two-dimensional spin 1/2 systems. The theoretical line shapes are compared with experiments. In the case of the cuprates they explain mid-infrared peaks observed in the insulator. In the case of the nickelates a predicted line shape is also shown to agree with the experiments. They discuss the possibility to observe this excitations in other experiments.

  3. Biometrics via IR spectroscopy of the epidermis: potential and difficulties

    NASA Astrophysics Data System (ADS)

    Mackie, David M.

    2012-06-01

    We discuss the potential and difficulties of using infrared (IR) spectroscopy of the human epidermis as a biometric. We present preliminary data on the fingerpads of 9 individuals demonstrating the potential for uniqueness and stability. We also present data on the challenges presented by complications such as sebum changes, intra-individual location variability, and skin care products.

  4. Gas in scattering media absorption spectroscopy - GASMAS

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2008-09-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. GASMAS combines narrow-band diode-laser spectroscopy with diffuse media optical propagation. While solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures, typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen. Also other dynamic processes such as drying of materials can be studied. The techniques have also been extended to remote-sensing applications (LIDAR-GASMAS).

  5. Distinction of three wood species by Fourier transform infrared spectroscopy and two-dimensional correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Anmin; Zhou, Qun; Liu, Junliang; Fei, Benhua; Sun, Suqin

    2008-07-01

    Dalbergia odorifera T. Chen, Pterocarpus santalinus L.F. and Pterocarpus soyauxii are three kinds of the most valuable wood species, which are hard to distinguish. In this paper, differentiation of D. odorifera, P. santalinus and P. soyauxii was carried out by using Fourier transform infrared spectroscopy (FT-IR), second derivative IR spectra and two-dimensional correlation infrared (2D-IR) spectroscopy. The three woods have their characteristic peaks in conventional IR spectra. For example, D. odorifera has obvious absorption peaks at 1640 and 1612 cm -1; P. santalinus has only one peak at 1614 cm -1; and P. soyauxii has one peak at 1619 cm -1 and one shoulder peak at 1597 cm -1. To enhance spectrum resolution and amplify the differences between the IR spectra of different woods, the second derivative technology was adopted to examine the three wood samples. More differences could be observed in the region of 800-1700 cm -1. Then, the thermal perturbation is applied to distinguish different wood samples in an easier way, because of the spectral resolution being enhanced by the 2D correlation spectroscopy. In the region of 1300-1800 cm -1, D. odorifera has five auto-peaks at 1518, 1575, 1594, 1620 and 1667 cm -1; P. santalinus has four auto-peaks at 1469, 1518, 1627 and 1639 cm -1 and P. soyauxii has only two auto-peaks at 1627 and 1639 cm -1. It is proved that the 2D correlation IR spectroscopy can be a new method to distinguish D. odorifera, P. santalinus and P. soyauxii.

  6. Aerosol optical absorption measurements with photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Kun; Wang, Lei; Liu, Qiang; Wang, Guishi; Tan, Tu; Zhang, Weijun; Chen, Weidong; Gao, Xiaoming

    2015-04-01

    Many parameters related to radiative forcing in climate research are known only with large uncertainties. And one of the largest uncertainties in global radiative forcing is the contribution from aerosols. Aerosols can scatter or absorb the electromagnetic radiation, thus may have negative or positive effects on the radiative forcing of the atmosphere, respectively [1]. And the magnitude of the effect is directly related to the quantity of light absorbed by aerosols [2,3]. Thus, sensitivity and precision measurement of aerosol optical absorption is crucial for climate research. Photoacoustic spectroscopy (PAS) is commonly recognized as one of the best candidates to measure the light absorption of aerosols [4]. A PAS based sensor for aerosol optical absorption measurement was developed. A 532 nm semiconductor laser with an effective power of 160 mW was used as a light source of the PAS sensor. The PAS sensor was calibrated by using known concentration NO2. The minimum detectable optical absorption coefficient (OAC) of aerosol was determined to be 1 Mm-1. 24 hours continues measurement of OAC of aerosol in the ambient air was carried out. And a novel three wavelength PAS aerosol OAC sensor is in development for analysis of aerosol wavelength-dependent absorption Angstrom coefficient. Reference [1] U. Lohmann and J. Feichter, Global indirect aerosol effects: a review, Atmos. Chem. Phys. 5, 715-737 (2005) [2] M. Z. Jacobson, Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols, Nature 409, 695-697 (2001) [3] V. Ramanathan and G. Carmichae, Global and regional climate changes due to black carbon, nature geoscience 1, 221-227 (2008) [4] W.P Arnott, H. Moosmuller, C. F. Rogers, T. Jin, and R. Bruch, Photoacoustic spectrometer for measuring light absorption by aerosol: instrument description. Atmos. Environ. 33, 2845-2852 (1999).

  7. 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

  8. Water in the Earth's Mantle: Mineral-specific IR Absorption Coefficients and Radiative Thermal Conductivities

    NASA Astrophysics Data System (ADS)

    Thomas, S. M.

    2015-12-01

    Minor and trace element chemistry, phase relations, rheology, thermal structure and the role of volatiles and their abundance in the deep Earth mantle are still far from fully explored, but fundamental to understanding the processes involved in Earth formation and evolution. Theory and high pressure experiments imply a significant water storage capacity of nominally anhydrous minerals, such as majoritic garnet, olivine, wadsleyite and ringwoodite, composing the Earth's upper mantle and transition zone to a depth of 660 km. Studying the effect of water incorporation on chemical and physical mineral properties is of importance, because the presence of trace amounts of water, incorporated as OH through charge-coupled chemical substitutions into such nominally anhydrous high-pressure silicates, notably influences phase relations, melting behavior, conductivity, elasticity, viscosity and rheology. Knowledge of absolute water contents in nominally anhydrous minerals is essential for modeling the Earth's interior water cycle. One of the most common and sensitive tools for water quantification is IR spectroscopy for which mineral-specific absorption coefficients are required. Such calibration constants can be derived from hydrogen concentrations determined by independent techniques, such as secondary ion mass spectrometry, Raman spectroscopy or proton-proton(pp)-scattering. Here, analytical advances and mineral-specific IR absorption coefficients for the quantification of H2O in major phases of the Earth's mantle will be discussed. Furthermore, new data from optical absorption measurements in resistively heated diamond-anvil cells at high pressures and temperatures up to 1000 K will be presented. Experiments were performed on synthetic single-crystals of olivine, ringwoodite, majoritic garnet, and Al-bearing phase D with varying iron, aluminum and OH contents to calculate radiative thermal conductivities and study their contribution to heat transfer in the Earth's interior

  9. Discrimination of Chinese Sauce liquor using FT-IR and two-dimensional correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Su-Qin; Li, Chang-Wen; Wei, Ji-Ping; Zhou, Qun; Noda, Isao

    2006-11-01

    We applied the three-step IR macro-fingerprint identification method to obtain the IR characteristic fingerprints of so-called Chinese Sauce liquor (Moutai liquor and Kinsly liquor) and a counterfeit Moutai. These fingerprints can be used for the identification and discrimination of similar liquor products. The comparison of their conventional IR spectra, as the first step of identification, shows that the primary difference in Sauce liquor is the intensity of characteristic peaks at 1592 and 1225 cm -1. The comparison of the second derivative IR spectra, as the second step of identification, shows that the characteristic absorption in 1400-1800 cm -1 is substantially different. The comparison of 2D-IR correlation spectra, as the third and final step of identification, can discriminate the liquors from another direction. Furthermore, the method was successfully applied to the discrimination of a counterfeit Moutai from the genuine Sauce liquor. The success of the three-step IR macro-fingerprint identification to provide a rapid and effective method for the identification of Chinese liquor suggests the potential extension of this technique to the identification and discrimination of other wine and spirits, as well.

  10. Evanescent wave sensors for mid-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Korsakova, S. V.; Romanova, E. A.

    2016-04-01

    An important problem of investigation of the air and water contamination by the mid-IR spectroscopy is discussed. A model of evanescent wave sensor made of a multimode waveguide transparent in the mid-IR spectral range is developed. Transmittance and sensitivity of a sensing element consisting of an input chalcogenide waveguide and a sensing waveguide depend on distribution of the guided modes amplitudes in the sensing waveguide. We have demonstrated that excitation of higher-order modes is important for optimal performance of such a sensor.

  11. Tomographic laser absorption spectroscopy using Tikhonov regularization.

    PubMed

    Guha, Avishek; Schoegl, Ingmar

    2014-12-01

    The application of tunable diode laser absorption spectroscopy (TDLAS) to flames with nonhomogeneous temperature and concentration fields is an area where only few studies exist. Experimental work explores the performance of tomographic reconstructions of species concentration and temperature profiles from wavelength-modulated TDLAS measurements within the plume of an axisymmetric McKenna burner. Water vapor transitions at 1391.67 and 1442.67 nm are probed using calibration-free wavelength modulation spectroscopy with second harmonic detection (WMS-2f). A single collimated laser beam is swept parallel to the burner surface, where scans yield pairs of line-of-sight (LOS) data at multiple radial locations. Radial profiles of absorption data are reconstructed using Tikhonov regularized Abel inversion, which suppresses the amplification of experimental noise that is typically observed for reconstructions with high spatial resolution. Based on spectral data reconstructions, temperatures and mole fractions are calculated point-by-point. Here, a least-squares approach addresses difficulties due to modulation depths that cannot be universally optimized due to a nonuniform domain. Experimental results show successful reconstructions of temperature and mole fraction profiles based on two-transition, nonoptimally modulated WMS-2f and Tikhonov regularized Abel inversion, and thus validate the technique as a viable diagnostic tool for flame measurements. PMID:25607968

  12. Gas-phase absorption cross sections of 24 monocyclic aromatic hydrocarbons in the UV and IR spectral ranges

    NASA Astrophysics Data System (ADS)

    Etzkorn, Thomas; Klotz, Björn; Sørensen, Søren; Patroescu, Iulia V.; Barnes, Ian; Becker, Karl H.; Platt, Ulrich

    Absorption cross sections of 24 volatile and non-volatile derivatives of benzene in the ultraviolet (UV) and the infrared (IR) regions of the electromagnetic spectrum have been determined using a 1080 l quartz cell. For the UV a 0.5 m Czerny-Turner spectrometer coupled with a photodiode array detector (spectral resolution 0.15 nm) was used. IR spectra were recorded with an FT-IR spectrometer (Bruker IFS-88, spectral resolution 1 cm -1). Absolute absorption cross sections and the instrument function are given for the UV, while for the IR, absorption cross sections and integrated band intensities are reported. The study focused primarily on the atmospherically relevant methylated benzenes (benzene, toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, styrene) and their ring retaining oxidation products (benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4,6-trimethylphenol and ( E,Z)- and ( E,E)-2,4-hexadienedial). The UV absorption cross sections reported here can be used for the evaluation of DOAS spectra (Differential Optical Absorption Spectroscopy) for measurements of the above compounds in the atmosphere and in reaction chambers, while the IR absorption cross sections will primarily be useful in laboratory studies on atmospheric chemistry, where FT-IR spectrometry is an important tool.

  13. Temperature dependence of C-terminal carboxylic group IR absorptions in the amide I‧ region

    NASA Astrophysics Data System (ADS)

    Anderson, Benjamin A.; Literati, Alex; Ball, Borden; Kubelka, Jan

    2015-01-01

    Studies of structural changes in peptides and proteins using IR spectroscopy often rely on subtle changes in the amide I‧ band as a function of temperature. However, these changes can be obscured by the overlap with other absorptions, namely the side-chain and terminal carboxylic groups. The former were the subject of our previous report (Anderson et al., 2014). In this paper we investigate the IR spectra of the asymmetric stretch of α-carboxylic groups for amino acids representing all major types (Gly, Ala, Val, Leu, Ser, Thr, Asp, Glu, Lys, Asn, His, Trp, Pro) as well as the C-terminal groups of three dipeptides (Gly-Gly, Gly-Ala, Ala-Gly) in D2O at neutral pH. Experimental temperature dependent IR spectra were analyzed by fitting of both symmetric and asymmetric pseudo-Voigt functions. Qualitatively the spectra exhibit shifts to higher frequency, loss in intensity and narrowing with increased temperature, similar to that observed previously for the side-chain carboxylic groups of Asp. The observed dependence of the band parameters (frequency, intensity, width and shape) on temperature is in all cases linear: simple linear regression is therefore used to describe the spectral changes. The spectral parameters vary between individual amino acids and show systematic differences between the free amino acids and dipeptides, particularly in the absolute peak frequencies, but the temperature variations are comparable. The relative variations between the dipeptide spectral parameters are most sensitive to the C-terminal amino acid, and follow the trends observed in the free amino acid spectra. General rules for modeling the α-carboxylic IR absorption bands in peptides and proteins as the function of temperature are proposed.

  14. Fourier Transform Infrared Spectroscopy: Part II. Advantages of FT-IR.

    ERIC Educational Resources Information Center

    Perkins, W. D.

    1987-01-01

    This is Part II in a series on Fourier transform infrared spectroscopy (FT-IR). Described are various advantages of FT-IR spectroscopy including energy advantages, wavenumber accuracy, constant resolution, polarization effects, and stepping at grating changes. (RH)

  15. All-fiber mid-IR supercontinuum: a powerful new tool for IR-spectroscopy

    NASA Astrophysics Data System (ADS)

    Moselund, Peter M.; Huot, Laurent; Brooks, Chris D.

    2016-03-01

    spectroscopy has until now been greatly limited by the availability of lightsources. The choice has generally stood between a laser whose narrow spectrum limits flexibility or a globar, whose low brightness limits signal to noise ratio. Mid-IR supercontinuum sources, which can deliver an ultra-broad spectrum with a million times higher brightness than a globar, are now appearing to fill the performance gap between the traditional lightsources. The generation of a supercontinuum is a highly nonlinear process produced by high peak power pulses propagating through a nonlinear medium. Since the underlying processes are fundamentally random there will normally be some pulse to pulse fluctuation in the output light which can cause problems in spectroscopy. Most of the mid-IR supercontinuum sources shown to date have also been limited to pulse repetition rates of only a few tens of kilohertz which makes it difficult to apply them to the popular FTIR spectroscopy techniques. Here we will demonstrate a fully packaged, all-fiber, turn-key, low noise, 4.8W, 1.8-4.2 μm supercontinuum source, which can operate with variable repetition rates of up to 30 MHz. In addition we will discuss ways to reduce and counter the effects of pulse fluctuations and we demonstrate optimization of the output spectrum of the source for various applications. Such a source can give any mid-IR optics lab access to a performance which has previously only been available from dedicated beamlines at huge synchrotron facilities.

  16. Atmospheric Measurements by Cavity Enhanced Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yi, Hongming; Wu, Tao; Coeur-Tourneur, Cécile; Fertein, Eric; Gao, Xiaoming; Zhao, Weixiong; Zhang, Weijun; Chen, Weidong

    2015-04-01

    Since the last decade, atmospheric environmental monitoring has benefited from the development of novel spectroscopic measurement techniques owing to the significant breakthroughs in photonic technology from the UV to the infrared spectral domain [1]. In this presentation, we will overview our recent development and applications of cavity enhanced absorption spectroscopy techniques for in situ optical monitoring of chemically reactive atmospheric species (such as HONO, NO3, NO2, N2O5) in intensive campaigns [2] and/or in smog chamber studies [3]. These field deployments demonstrated that modern photonic technologies (newly emergent light sources combined with high sensitivity spectroscopic techniques) can provide a useful tool to improve our understanding of tropospheric chemical processes which affect climate, air quality, and the spread of pollution. Experimental detail and preliminary results will be presented. Acknowledgements. The financial support from the French Agence Nationale de la Recherche (ANR) under the NexCILAS (ANR-11-NS09-0002) and the CaPPA (ANR-10-LABX-005) contracts is acknowledged. References [1] X. Cui, C. Lengignon, T. Wu, W. Zhao, G. Wysocki, E. Fertein, C. Coeur, A. Cassez,L. Croisé, W. Chen, et al., "Photonic Sensing of the Atmosphere by absorption spectroscopy", J. Quant. Spectrosc. Rad. Transfer 113 (2012) 1300-1316 [2] T. Wu, Q. Zha, W. Chen, Z. XU, T. Wang, X. He, "Development and deployment of a cavity enhanced UV-LED spectrometer for measurements of atmospheric HONO and NO2 in Hong Kong", Atmos. Environ. 95 (2014) 544-551 [3] T. Wu, C. Coeur-Tourneur, G. Dhont,A. Cassez, E. Fertein, X. He, W. Chen,"Application of IBBCEAS to kinetic study of NO3 radical formation from O3 + NO2 reaction in an atmospheric simulation chamber", J. Quant. Spectrosc. Rad. Transfer 133 (2014)199-205

  17. Early fire sensing using near-IR diode laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Bomse, David S.; Hovde, D. Christian; Chen, Shin-Juh; Silver, Joel A.

    2002-09-01

    We describe research leading to a trace gas detection system based on optical absorption using near-IR diode lasers that is intended to provide early warning of incipient fires. Applications include "high loss" structures such as office buildings, hospitals, hotels and shopping malls as well as airplanes and manned spacecraft where convention smoke detectors generate unacceptably high false alarm rates. Simultaneous or near-simultaneous detection of several gases (typically carbon dioxide, carbon monoxide, acetylene and hydrogen cyanide) provides high sensitivity while reducing the chance of false alarms. Continuous measurement of carbon dioxide concentrations also provides an internal check of instrument performance because ambient levels will not drop below ~350 ppm.

  18. Non-destructive plant health sensing using absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Bledsoe, Jim; Manukian, Ara; Pearce, Michael; Weiss, Lee

    1988-01-01

    The sensor group of the 1988 EGM 4001 class, working on NASA's Controlled Ecological Life Support Systems (CELSS) project, investigated many different plant health indicators and the technologies used to test them. The project selected by the group was to measure chlorophyll levels using absorption spectroscopy. The spectrometer measures the amount of chlorophyll in a leaf by measuring the intensity of light of a specific wavelength that is passed through a leaf. The three wavelengths of light being used corresponded to the near-IR absorption peaks of chlorophyll a, chlorophyll b, and chlorophyll-free structures. Experimentation showed that the sensor is indeed measuring levels of chlorophyll a and b and their changes before the human eye can see any changes. The detector clamp causes little damage to the leaf and will give fairly accurate readings on similar locations on a leaf, freeing the clamp from having to remain on the same spot of a leaf for all measurements. External light affects the readings only slightly so that measurements may be taken in light or dark environments. Future designs and experimentation will concentrate on reducing the size of the sensor and adapting it to a wider range of plants.

  19. IR/THz Double Resonance Spectroscopy Approach for Remote Chemical Detection at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Tanner, Elizabeth A.; Phillips, Dane J.; De Lucia, Frank C.; Everitt, Henry O.

    2013-06-01

    A remote sensing methodology based on infrared/terahertz (IR/THz) double resonance (DR) spectroscopy is shown to overcome limitations traditionally associated with either IR or THz spectroscopic approaches for detecting trace gases in an atmosphere. The applicability of IR/THz DR spectroscopy is explored by estimating the IR and THz power requirements for detecting a 100 part-per-million-meter cloud of methyl fluoride, methyl chloride, or methyl bromide at ranges up to 1km in three atmospheric windows below 0.3 THz. These prototypical molecules are used to ascertain the dependence of the DR signal-to-noise ratio on IR and THz beam power. A line-tunable CO_2 laser with 100 ps pulse duration generates a DR signature in four rotational transitions on a time scale commensurate with collisional relaxations caused by atmospheric N_2 and O_2. A continuous wave THz beam is frequency tuned to probe one of these rotational transitions so that laser-induced absorption variations in the analyte cloud are detected as temporal power fluctuations synchronized with the laser pulses. A combination of molecule-specific physics and scenario-dependent atmospheric conditions are used to predict the signal-to-noise ratio (SNR) for detecting an analyte as a function of cloud column density. A methodology is presented by which the optimal IR/THz pump/probe frequencies are identified. These estimates show the potential for low concentration chemical detection in a challenging atmospheric scenario with currently available or near term hardware components.

  20. Determination of Cellulose Fiber Structure Using IR Reflectance Spectroscopy of Paper

    NASA Astrophysics Data System (ADS)

    Derkacheva, O. Yu.

    2015-01-01

    A rapid and non-destructive method for analyzing the structure of cellulose fibers using IR reflectance spectroscopy from a paper surface was developed and verified for correctness. IR absorption and reflectance spectra of standard paper samples of known composition (sheets made of four fibers of different origin without additives and with additives of kaolin and chalk) were analyzed. Good correlations between these two spectral methods were found for the studied samples. Calibration curves were useful for assessing the structure of cellulose samples from XVIth century historical paper. Data on the degree of cellulose ordering that were obtained from the paper reflectance spectra indicated that the studied sheets consisted mainly of flax fibers with added cotton. This agreed fully with the historical fact that the studied samples were rag papers.

  1. Mid-IR laser absorption diagnostics for hydrocarbon vapor sensing in harsh environments

    NASA Astrophysics Data System (ADS)

    Klingbeil, Adam Edgar

    unburned fuel, engine performance can be characterized and future engine designs can be improved to utilize all of the fuel supplied to the engine. Simultaneous measurement of absorption at two wavelengths is used as a basis for hydrocarbon detection in severe environments. A novel wavelength-tunable mid-IR laser is modified to rapidly switch between two wavelengths, improving the versatility of this laser system. The two-wavelength technique is then exploited to measure vapor concentration while rejecting interferences such as scattering from liquid droplets and absorption from other species. This two-wavelength laser is also used to simultaneously determine temperature and vapor concentration. These techniques, in combination with the library of temperature-dependent hydrocarbon spectra, lay the groundwork necessary to develop fuel diagnostics for laboratory experiments and tests in pulse detonation engines and internal combustion engines. The temperature-dependent spectroscopy of gasoline is examined to develop a sensor for fuel/air ratio in an internal combustion engine. A wavelength was selected for good sensitivity to gasoline concentration. A spectroscopic model is developed that uses the relative concentrations of five structural classes to predict the absorption spectrum of gasoline samples with varying composition. The model is tested on 21 samples of gasoline for temperatures ranging from 300 to 1200 K, showing good agreement between model and measurements over the entire temperature range. Finally, a two-wavelength diagnostic was developed to measure the post-evaporation temperature and n-dodecane concentration in an aerosol-laden shock tube. The experimental data validate a model which calculates the effects of shock-wave compression on a two-phase mixture. The measured post-shock temperature and vapor concentration compare favorably for gas-phase and aerosol experiments. The agreement between the two fuel-loading techniques verifies that this aerosol shock

  2. Sensitive far-IR survey spectroscopy: BLISS for SPICA

    NASA Astrophysics Data System (ADS)

    Bradford, C. M.; Kenyon, Matt; Holmes, Warren; Bock, James; Koch, Timothy

    2008-07-01

    We present a concept for BLISS, a sensitive far-IR-submillimeter spectrograph for SPICA. SPICA is a JAXA-led mission featuring a 3.5-meter telescope actively cooled to below 5K, envisioned for launch in 2017. The low-background platform is especially compelling for moderate-resolution survey spectroscopy, for which BLISS is designed. The BLISS / SPICA combination will offer line sensitivities below 10-20W m-2 in modest integrations, enabling rapid survey spectroscopy of galaxies out to redshift 5. The far-IR fine-structure and molecular transitions which BLISS / SPICA will measure are immune to dust extinction, and will unambiguously reveal these galaxies' redshifts, stellar and AGN contents, gas properties, and heavy-element abundances. Taken together, such spectra will reveal the history of galaxies from 1 GY after the Big Bang to the present day. BLISS is comprised of five sub-bands, each with two R ~ 700 grating spectrometer modules. The modules are configured with polarizing and dichroic splitters to provide complete instantaneous spectral coverage in two sky positions. To approach background-limited performance, BLISS detectors must have sensitivities at or below 5 × 10-20W Hz-1/2, and the format is 10 arrays of several hundred pixels each. It is anticipated that these requirements can be met on SPICA's timescale with leg-isolated superconducting (TES) bolometers cooled with a 50 mK magnetic refrigerator.

  3. Ultradeep Spectroscopy with the Spitzer^1 IRS^2

    NASA Astrophysics Data System (ADS)

    Teplitz, H. I.; Desai, V.; Armus, L.; Chary, R.; Colbert, J. W.; Frayer, D. T.; Pope, A.; Blain, A.; Spoon, H.; Charmandaris, V.; Scott, D.; Antonucci, S.

    2008-03-01

    Mid-IR spectroscopy has detected the signatures of star-formation (PAH emission) in high redshift (z>1) ultra- and hyper-luminous infrared galaxies. However, the study of the dominant population of IR-luminous galaxies (10^{11} - 10^{12} Lsun at 1IRS) on the Spitzer Space Telescope. We targeted two faint (˜ 0.15 mJy) sources in the Southern GOODS field at z=1.09 and z=2.69 as likely star-forming galaxies. Spectra of the lower redshift target were taken in 8-21 micron range (short-low first order and long-low second order), while the higher redshift target was observed from 21-37 microns (long-low first order). Observing times were 3 and 9 hours on-source for SL-1 and LL-2, respectively, and 12 hours for LL-1. We also present the spectra of two serendipitous sources. We detect strong PAH emission in four targets. We compare the spectra to those of local galaxies observed by the IRS. The z=1.09 source appears to be a typical, star-formation dominated LIRG, while the z=2.69 source is a composite source with strong star formation and a prominent AGN. The AGN component dominates the IRAC colors of this source, obscuring the 1.6 micron ``bump.'' Such sources would be excluded from IRAC surveys for starbursts which might then underestimate the star formation density.

  4. IR absorptions of C60(+) and C60(-) in neon matrixes.

    PubMed

    Kern, Bastian; Strelnikov, Dmitry; Weis, Patrick; Böttcher, Artur; Kappes, Manfred M

    2013-08-29

    C60(+) ions were produced by electron-impact ionization of sublimed C60, collimated into an ion beam, turned 90° by an electrostatic deflector to separate them from neutrals, mass filtered by a radio frequency quadrupole, and co-deposited with Ne on a cold 5 K gold-coated sapphire substrate. Infrared absorption spectroscopy revealed the additional presence of C60 and C60(-) in the as-prepared cryogenic matrixes. To change the C60(+)/C60(-) ratio, CCl4 or CO2 electron scavengers were added to the matrix gas. Also taking into account DFT calculations, we have identified nine new previously unpublished IR absorptions of C60(+) and seven of C60(-) in Ne matrixes. Our measurements are in very good agreement with DFT calculations, predicting D5d C60(+) and D3d C60(-) ground states. The new results may be of interest regarding the presence of C60 and C70 (as well as ions thereof) in Space. PMID:23902528

  5. Rapid identification of Chinese Sauce liquor from different fermentation positions with FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Changwen; Wei, Jiping; Zhou, Qun; Sun, Suqin

    2008-07-01

    FT-IR and two-dimensional correlation spectroscopy (2D-IR) technology were applied to discriminate Chinese Sauce liquor from different fermentation positions (top, middle and bottom of fermentation cellar) for the first time. The liquors at top, middle and bottom of fermentation cellar, possessed the characteristic peaks at 1731 cm -1, 1733 cm -1 and 1602 cm -1, respectively. In the 2D correlation infrared spectra, the differences were amplified. A strong auto-peak at 1725 cm -1 showed in the 2D spectra of the Top Liquor, which indicated that the liquor might contain some ester compounds. Different from Top Liquor, three auto-peaks at 1695, 1590 and 1480 cm -1 were identified in 2D spectra of Middle Liquor, which were the characteristic absorption of acid, lactate. In 2D spectra of Bottom Liquor, two auto-peaks at 1570 and 1485 cm -1 indicated that lactate was the major component. As a result, FT-IR and 2D-IR correlation spectra technology provided a rapid and effective method for the quality analysis of the Sauce liquor.

  6. Differentiation of Leishmania species by FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Aguiar, Josafá C.; Mittmann, Josane; Ferreira, Isabelle; Ferreira-Strixino, Juliana; Raniero, Leandro

    2015-05-01

    Leishmaniasis is a parasitic infectious disease caused by protozoa that belong to the genus Leishmania. It is transmitted by the bite of an infected female Sand fly. The disease is endemic in 88 countries Desjeux (2001) [1] (16 developed countries and 72 developing countries) on four continents. In Brazil, epidemiological data show the disease is present in all Brazilian regions, with the highest incidences in the North and Northeast. There are several methods used to diagnose leishmaniasis, but these procedures have many limitations, are time consuming, have low sensitivity, and are expensive. In this context, Fourier Transform Infrared Spectroscopy (FT-IR) analysis has the potential to provide rapid results and may be adapted for a clinical test with high sensitivity and specificity. In this work, FT-IR was used as a tool to investigate the promastigotes of Leishmaniaamazonensis, Leishmaniachagasi, and Leishmaniamajor species. The spectra were analyzed by cluster analysis and deconvolution procedure base on spectra second derivatives. Results: cluster analysis found four specific regions that are able to identify the Leishmania species. The dendrogram representation clearly indicates the heterogeneity among Leishmania species. The band deconvolution done by the curve fitting in these regions quantitatively differentiated the polysaccharides, amide III, phospholipids, proteins, and nucleic acids. L. chagasi and L. major showed a greater biochemistry similarity and have three bands that were not registered in L. amazonensis. The L. amazonensis presented three specific bands that were not recorded in the other two species. It is evident that the FT-IR method is an indispensable tool to discriminate these parasites. The high sensitivity and specificity of this technique opens up the possibilities for further studies about characterization of other microorganisms.

  7. Using Fourier transform IR spectroscopy to analyze biological materials

    PubMed Central

    Baker, Matthew J; Trevisan, Júlio; Bassan, Paul; Bhargava, Rohit; Butler, Holly J; Dorling, Konrad M; Fielden, Peter R; Fogarty, Simon W; Fullwood, Nigel J; Heys, Kelly A; Hughes, Caryn; Lasch, Peter; Martin-Hirsch, Pierre L; Obinaju, Blessing; Sockalingum, Ganesh D; Sulé-Suso, Josep; Strong, Rebecca J; Walsh, Michael J; Wood, Bayden R; Gardner, Peter; Martin, Francis L

    2015-01-01

    IR spectroscopy is an excellent method for biological analyses. It enables the nonperturbative, label-free extraction of biochemical information and images toward diagnosis and the assessment of cell functionality. Although not strictly microscopy in the conventional sense, it allows the construction of images of tissue or cell architecture by the passing of spectral data through a variety of computational algorithms. Because such images are constructed from fingerprint spectra, the notion is that they can be an objective reflection of the underlying health status of the analyzed sample. One of the major difficulties in the field has been determining a consensus on spectral pre-processing and data analysis. This manuscript brings together as coauthors some of the leaders in this field to allow the standardization of methods and procedures for adapting a multistage approach to a methodology that can be applied to a variety of cell biological questions or used within a clinical setting for disease screening or diagnosis. We describe a protocol for collecting IR spectra and images from biological samples (e.g., fixed cytology and tissue sections, live cells or biofluids) that assesses the instrumental options available, appropriate sample preparation, different sampling modes as well as important advances in spectral data acquisition. After acquisition, data processing consists of a sequence of steps including quality control, spectral pre-processing, feature extraction and classification of the supervised or unsupervised type. A typical experiment can be completed and analyzed within hours. Example results are presented on the use of IR spectra combined with multivariate data processing. PMID:24992094

  8. Stencil lithography of gold-black IR absorption coatings

    NASA Astrophysics Data System (ADS)

    Panjwani, Deep; Yesiltas, Mehmet; Singh, Simranjit; Barco, Enrique Del; Peale, R. E.; Hirschmugl, Carol; Sedlemair, Julia

    2014-09-01

    Gold black coatings are deposited through a stencil shadow mask to produce infrared-absorbing patterns with sub-mm lateral dimensions. Such dimensions match the characteristic pitch of Long Wave Infrared (LWIR) array bolometers. Infrared spectral imaging with sub-micron spatial resolution reveals the spatial distribution of absorption across the pattern.

  9. Near-IR Spectroscopy of Amalthea (JV) and Thebe (JXIV)

    NASA Astrophysics Data System (ADS)

    Bustani, D.; Bell, J. F., III; Veverka, J.; Brown, R. H.; Cruikshank, D. P.

    1997-07-01

    We used the NASA IRTF, the NSFCAM 256x256 InSb array camera, and the JPL Cooled Coronograph (CoCo) to obtain H and K spectra of the faint inner Jovian satellites Amalthea (JV, Mv=14.1) and Thebe (JXIV, Mv=15.7). The observations were obtained on 25 and 26 July 1996 UT, near Jupiter opposition, when the satellites had a maximum limb elongation of 36" (JV) and 49" (JXIV). CoCo was designed for imaging of faint sources in the vicinity of much brighter sources (e.g., stellar companions), but in order to further supress scattered light from Jupiter (an extended source ~ 10(4) times brighter than these faint satellites), we inserted a special hard mask aperture ahead of the NSFCAM/CoCo optical path. In order to obtain spectra with this setup we attached a crude ~ 2" wide razor-edge slit to the top of the hard mask. The resulting spectral resolution is moderate (R ~ 440 in H and R ~ 870 in K) and is adequate for initial near-IR survey spectra of these objects. We obtained 4 spectra each of JV and JXIV in H (1.44 to 1.98 mu m) and 4 spectra each of JV and JXIV in K (2.0 to 2.35 mu m), as well as comparison spectra of Titan, Mimas, two solar-type stars, and Ne and Kr wavelength calibration lamps. Our calibrated Titan and Mimas CoCo spectra are consistent with previous H and K measurements of these objects. Our preliminary spectra of Amalthea reveal a relatively featureless spectrum in the 1.44 to 1.98 mu m and 2.06 to 2.17 mu m regions, but show evidence for an as-yet unidentified absorption from 2.20 to 2.30 mu m, apparently centered near 2.27 mu m. Our preliminary spectra of Thebe reveal a relatively featureless spectrum from 1.44 to 1.65 mu m and from 2.00 to 2.27 mu m, but show evidence for an as-yet unidentified weak absorption from ~ 1.70 to ~ 1.80 mu m, centered near 1.75 mu m. Continued refinement of the reflectance and wavelength calibrations is proceeding, and possible origins and band assignments for these near-IR absorption features are being investigated.

  10. Application of Fourier-transform infrared (FT-ir) spectroscopy to in-situ studies of coal combustion

    SciTech Connect

    Ottesen, D K; Thorne, L R

    1982-04-01

    The feasibility of using Fourier-transform infrared (FT-ir) spectroscopy for in situ measurement of gas phase species concentrations and temperature during coal combustion is examined. This technique is evaluated in terms of its potential ability to monitor several important chemical and physical processes which occur in pulverized coal combustion. FT-ir absorption measurements of highly sooting, gaseous hydrocarbon/air flames are presented to demonstrate the fundamental usefulness of the technique for in situ detection of gas phase temperatures and species concentrations in high temperature combustion environments containing coal, char, mineral matter and soot particles. Preliminary results for coal/gaseous fuel/air flames are given.

  11. Indirect Terahertz Spectroscopy of Molecular Ions Using Highly Accurate and Precise Mid-Ir Spectroscopy

    NASA Astrophysics Data System (ADS)

    Mills, Andrew A.; Ford, Kyle B.; Kreckel, Holger; Perera, Manori; Crabtree, Kyle N.; McCall, Benjamin J.

    2009-06-01

    With the advent of Herschel and SOFIA, laboratory methods capable of providing molecular rest frequencies in the terahertz and sub-millimeter regime are increasingly important. As of yet, it has been difficult to perform spectroscopy in this wavelength region due to the limited availability of radiation sources, optics, and detectors. Our goal is to provide accurate THz rest frequencies for molecular ions by combining previously recorded microwave transitions with combination differences obtained from high precision mid-IR spectroscopy. We are constructing a Sensitive Resolved Ion Beam Spectroscopy setup which will harness the benefits of kinematic compression in a molecular ion beam to enable very high resolution spectroscopy. This ion beam is interrogated by continuous-wave cavity ringdown spectroscopy using a home-made widely tunable difference frequency laser that utilizes two near-IR lasers and a periodically-poled lithium niobate crystal. Here, we report our efforts to optimize our ion beam spectrometer and to perform high-precision and high-accuracy frequency measurements using an optical frequency comb. footnote

  12. Development of a Near-Ir Cavity Enhanced Absorption Spectrometer for the Detection of Atmospheric Oxidation Products and Organoamines

    NASA Astrophysics Data System (ADS)

    Eddingsaas, Nathan C.; Jewell, Breanna; Thurnherr, Emily

    2014-06-01

    An estimated 10,000 to 100,000 different compounds have been measured in the atmosphere, each one undergoes many oxidation reactions that may or may not degrade air quality. To date, the fate of even some of the most abundant hydrocarbons in the atmosphere is poorly understood. One difficulty is the detection of atmospheric oxidation products that are very labile and decompose during analysis. To study labile species under atmospheric conditions, a highly sensitive, non-destructive technique is needed. Here we describe a near-IR incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) setup that we are developing to meet this end. We have chosen to utilize the near-IR, where vibrational overtone absorptions are observed, due to the clean spectral windows and better spectral separation of absorption features. In one spectral window we can simultaneously and continuously monitor the composition of alcohols, hydroperoxides, and carboxylic acids in an air mass. In addition, we have used our CEAS setup to detect organoamines. The long effective path length of CEAS allows for low detection limits, even of the overtone absorption features, at ppb and ppt levels.

  13. Photoelectron and X-ray Absorption Spectroscopy Of Pu

    SciTech Connect

    Tobin, J; Chung, B; Schulze, R; Farr, J; Shuh, D

    2003-11-12

    We have performed Photoelectron Spectroscopy and X-Ray Absorption Spectroscopy upon highly radioactive samples of Plutonium at the Advanced Light Source in Berkeley, CA, USA. First results from alpha and delta Plutonium are reported as well as plans for future studies of actinide studies.

  14. Multiplexed absorption tomography with calibration-free wavelength modulation spectroscopy

    SciTech Connect

    Cai, Weiwei; Kaminski, Clemens F.

    2014-04-14

    We propose a multiplexed absorption tomography technique, which uses calibration-free wavelength modulation spectroscopy with tunable semiconductor lasers for the simultaneous imaging of temperature and species concentration in harsh combustion environments. Compared with the commonly used direct absorption spectroscopy (DAS) counterpart, the present variant enjoys better signal-to-noise ratios and requires no baseline fitting, a particularly desirable feature for high-pressure applications, where adjacent absorption features overlap and interfere severely. We present proof-of-concept numerical demonstrations of the technique using realistic phantom models of harsh combustion environments and prove that the proposed techniques outperform currently available tomography techniques based on DAS.

  15. Absorption and fluorescence spectroscopy on a smartphone

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  16. Composition of the Martian aerosols through near-IR spectroscopy

    NASA Technical Reports Server (NTRS)

    Erard, Stephane; Cerroni, Priscilla; Coradini, Angioletta

    1993-01-01

    Near-infrared spectroscopy is a powerful technique to study the composition of planetary surfaces, as the main minerals exhibit absorption bands in this spectral range. It gave important information on the mineralogy and petrology of Mars in the past twenty years although in this case it is well known that a large fraction of light is scattered by the airborne particles before reaching the surface. The measured signal is thus the sum of two different contributions that should be studied separately: One from the surface and one from the aerosols that depends on their density, size distribution and composition. Data from the ISM imaging spectrometer are used here to derive the aerosols spectrum. They consist in sets of spectra (from 0.76 to 3.16 microns) of approximately 3000 pixels approximately 25x25 sq km in size. The resulting spectrum exhibits both water-ice and clay mineral features superimposed on a scattering continuum.

  17. Applications of absorption spectroscopy using quantum cascade lasers.

    PubMed

    Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

    2014-01-01

    Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis. PMID:25239063

  18. Probing protonation sites of isolated flavins using IR spectroscopy: from lumichrome to the cofactor flavin mononucleotide.

    PubMed

    Langer, Judith; Günther, Alan; Seidenbecher, Sophie; Berden, Giel; Oomens, Jos; Dopfer, Otto

    2014-08-25

    Infrared spectra of the isolated protonated flavin molecules lumichrome, lumiflavin, riboflavin (vitamin B2), and the biologically important cofactor flavin mononucleotide are measured in the fingerprint region (600-1850 cm(-1)) by means of IR multiple-photon dissociation (IRMPD) spectroscopy. Using density functional theory calculations, the geometries, relative energies, and linear IR absorption spectra of several low-energy isomers are calculated. Comparison of the calculated IR spectra with the measured IRMPD spectra reveals that the N10 substituent on the isoalloxazine ring influences the protonation site of the flavin. Lumichrome, with a hydrogen substituent, is only stable as the N1-protonated tautomer and protonates at N5 of the pyrazine ring. The presence of the ribityl unit in riboflavin leads to protonation at N1 of the pyrimidinedione moiety, and methyl substitution in lumiflavin stabilizes the tautomer that is protonated at O2. In contrast, flavin mononucleotide exists as both the O2- and N1-protonated tautomers. The frequencies and relative intensities of the two C=O stretch vibrations in protonated flavins serve as reliable indicators for their protonation site. PMID:24895155

  19. Probing a Conformational Change of a Photoswitchable Allosteric Protein with Ultrafast IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Stucki-Buchli, Brigitte; Waldauer, Steven A.; Walser, Reto; Pfister, Rolf; Hamm, Peter

    2015-03-01

    By covalently linking an azobenzene photoswitch across the binding groove of an allosteric protein domain, a conformational transition can be initiated by a laser pulse.. This transition mimics the conformational change of the unmodified domain upon ligand binding. We have studied this light induced conformational change by ultrafast IR spectroscopy. So far, we have probed two IR absorption bands: First, the amide I band which arises from the carbonyl stretch vibration of all amide groups in the protein and is sensitive to overall structural changes, and second, a vibration localized on the photoswitch, which is sensitive to its local environment, namely the opening of the binding groove. We have found that the binding groove opens on a timescale of 100 ns in a non-exponential manner. Even after the binding groove has equilibrated, the protein conformation still continues to change elsewhere. Currently, we are incorporating site-specific IR labels, to learn more about the response of the protein to the perturbation of the binding groove.

  20. Infrared Absorption Spectroscopy Measurement of SOx using Tunable Infrared Laser

    NASA Astrophysics Data System (ADS)

    Fukuchi, Tetsuo

    The absorption characteristics of sulfur dioxide (SO2) and sulfur trioxide (SO3) in the infrared region were measured using a quantum cascade laser and an absorption cell of length 1 m heated to 150°C. The laser was scanned over the wavelength range 6.9-7.4 μm, which included the absorption bands of SO2 and SO3. Measurement results showed that the absorption bands of SO2 and SO3 partially overlapped, with peaks at 7.28 μm and 7.35 μm for SO2 and 7.14 μm and 7.25 μm for SO3. These results showed the possbility of using infrared laser absorption spectroscopy for measurement of sulfur oxides (SOx) in flue gas. For SO3 measurement, infrared absorption spectroscopy was shown to be more suitable than ultraviolet absorption spectroscopy. The absorption characteristics of open air in the same wavelength region showed that the interference due to water vapor must be efficiently removed to perform SOx measurement in flue gas.

  1. Ir Spectroscopy of Selected Atmospheric Monoterpenes and Oxydation Products

    NASA Astrophysics Data System (ADS)

    Aviles Moreno, Juan-Ramon; Huet, T. R.; Goubet, Manuel; Soulard, Pascale; Asselin, Pierre; Georges, Robert; Pirali, Olivier; Roy, P.

    2014-06-01

    Several monoterpenes are biogenic volatile organic compounds (BVOCS) present in the atmosphere. They can react with OH, O_3, NO_x, etc. to give rise to several oxydation and degradation products. We have studied the gas phase spectroscopy of monocyclic (limonene, γ-terpinene) and bicyclic (α-pinene, β-pinene) atmospheric monoterpenes (C10H_{16}), as well as two C10H_{14O} oxydation products (perillaldehyde, carvone). In the first step of this work, theoretical calculations and microwave spectroscopy were used in order to evidence the most stable conformers and their relative energies. In the present communication we will present the results of the IR study. Infrared spectra have been recorded on the FTIR spectrometer of the AILES beamline at synchrotron SOLEIL, using the Jet-AILES molecular beam and a long path cell. Special attention was given to the 700-1300 wn atmospheric window, to the CH vibration region, and to the "finger print" FIR region. Quantum calculations have been performed at different levels of theory (DFT, ab initio). In particular anharmonic force fields were obtained in order to model the vibrational structures. J. R. Aviles Moreno, F. Partal Urena, J. J. Lopez Gonzalez and T. R. Huet, C. Phys. Lett. 473 (2009) 17 J. R. Aviles Moreno, T. R. Huet, F. Partal Urena, J. J. Lopez Gonzalez, Struc. Chem. 24 (2013) 1163 J. R. Aviles Moreno, E. Neeman, T. R. Huet, manuscript in preparation Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged. The experiment on the AILES beam-line at synchrotron SOLEIL was performed under project number 20130192.

  2. [Study of retrieving formaldehyde with differential optical absorption spectroscopy].

    PubMed

    Li, Yu-Jin; Xie, Pin-Hua; Qin, Min; Qu, Xiao-Ying; Hu, Lin

    2009-01-01

    The present paper introduces the method of retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS). The authors measured ambient HCHO in Beijing region with the help of differential optical absorption spectroscopy instrument made by ourself, and discussed numerous factors in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), especially, the choice of HCHO wave band, how to avoid absorption of ambient SO2, NO2 and O3, and the influence of the Xenon lamp spectrum structure on the absorption of ambient HCHO. The authors achieved the HCHO concentration by simultaneously retrieving the concentrations of HCHO, SO2, NO2 and O3 with non-linear least square fitting method, avoiding the effect of choosing narrow wave of HCHO and the residual of SO2, NO2, O3 and the Xenon lamp spectrum structure in retrieving process to attain the concentration of HCHO, Finally the authors analyzed the origin of error in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), and the total error is within 13.7% in this method. PMID:19385238

  3. Study of a V-shape flame based on IR spectroscopy and IR imaging

    NASA Astrophysics Data System (ADS)

    Pouplin, J.; Collin, A.; Acem, Z.; Parent, G.; Boulet, P.; Vena, P.; Galizzi, C.; Kühni, M.; André, F.; Escudié, D.

    2016-01-01

    Applicability of an IR imaging/spectroscopy diagnostic was tested on a laboratory- scale flame. For this purpose, measurements were carried out on a V-shape flame developed along a wall, with the aim of evaluating the wall temperature and of identifying the flame properties (temperature and species concentrations). Infrared measurements with a multiband camera and a spectrometer were post-processed and compared, in particular, with thermocouple measurements carried out for the wall temperature. Simple evaluation involving a correction for the emissivity showed a quite good agreement when assessed against experimental data. An attempt to reconstruct a flame emission spectrum was also carried out, expecting a possible inverse identification of the flame properties. The method showed a promising behaviour on synthetic data built with a radiative transfer model for gas and wall radiation. However, the spectrum reconstruction method is not yet accurate enough to allow an identification of the flame properties in full confidence when applied to actual experimental data. First tests showed a correct qualitative behaviour, but model refinements are required at least for the flame radiation, before getting accurate flame properties.

  4. Plant Sunscreens in Nature: UV and IR Spectroscopy of Sinapate Derivatives

    NASA Astrophysics Data System (ADS)

    Dean, Jacob C.; Walsh, Patrick S.; Zwier, Timothy S.; Allais, Florent

    2013-06-01

    Plants are exposed to prolonged amounts of UV radiation, with elevated levels of UV-B (280-320 nm) as the ozone layer is depleted. When UV-B radiation penetrates the leaf epidermis, substantial oxidative damage can occur to plant tissues and plant growth can be inhibited. Sinapate esters, particularly sinapoyl malate, have been shown to efficiently prevent such damaging effects. By studying a series of molecules in this unique class under the isolated, cold conditions of a supersonic expansion, the fundamental UV-spectroscopic properties and photophysical aspects following UV absorption can be interrogated in detail. Sinapic acid and neutral sinapoyl malate were brought into the gas phase by laser desorption and detected via resonant two-photon ionization (R2PI). IR-UV double resonance methods were employed to obtain single-conformation UV and IR spectra. As the UV chromophore of interest is the sinapoyl moiety, sinapic acid served as the simplest model to compare directly to the more functionalized sinapoyl malate. It has a spectrum much like most aromatics, with a strong {ππ}^* origin, and well-resolved vibronic structure. By contrast, the spectrum for sinapoyl malate displays a large, broad absorption with little resolved vibronic structure, reflecting its role in nature as a pivotal and efficient UV protectant for plants, serving as the plant's sunscreen. Using conformer-specific IR spectroscopy, the individual conformations of both species were assigned and used as the basis for further ab initio calculations of the excited states that give rise to the observed behavior. Landry, L.G.; Chapple, C.S.; Last, R.L. Plant Physiol. {1995}, 109, 1159-1166.

  5. Atomic absorption spectroscopy with high temperature flames.

    PubMed

    Willis, J B

    1968-07-01

    An account is given of the history of the development of high temperature flames for the atomic absorption measurement of metals forming refractory oxides. The principles governing the design of premix burners for such flames, and the relative merits of different types of nebulizer burner systems are described. After a brief account of the structure and emission characteristics of the premixed oxygen-acetylene and nitrous oxide-acetylene flames, the scope and limitations of the latter flame in chemical analysis are discussed. PMID:20068790

  6. Single-particle absorption spectroscopy by photothermal contrast.

    PubMed

    Yorulmaz, Mustafa; Nizzero, Sara; Hoggard, Anneli; Wang, Lin-Yung; Cai, Yi-Yu; Su, Man-Nung; Chang, Wei-Shun; Link, Stephan

    2015-05-13

    Removing effects of sample heterogeneity through single-molecule and single-particle techniques has advanced many fields. While background free luminescence and scattering spectroscopy is widely used, recording the absorption spectrum only is rather difficult. Here we present an approach capable of recording pure absorption spectra of individual nanostructures. We demonstrate the implementation of single-particle absorption spectroscopy on strongly scattering plasmonic nanoparticles by combining photothermal microscopy with a supercontinuum laser and an innovative calibration procedure that accounts for chromatic aberrations and wavelength-dependent excitation powers. Comparison of the absorption spectra to the scattering spectra of the same individual gold nanoparticles reveals the blueshift of the absorption spectra, as predicted by Mie theory but previously not detectable in extinction measurements that measure the sum of absorption and scattering. By covering a wavelength range of 300 nm, we are furthermore able to record absorption spectra of single gold nanorods with different aspect ratios. We find that the spectral shift between absorption and scattering for the longitudinal plasmon resonance decreases as a function of nanorod aspect ratio, which is in agreement with simulations. PMID:25849105

  7. IR fiber-optic evanescent wave spectroscopy (FEWS) for sensing applications (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Katzir, Abraham

    2016-03-01

    We developed crystalline AgClBr fibers of diameters 0.7-0.9mm that are flexible, non-toxic, insoluble in water and highly transparent between 4-15µm. We used these fibers for various sensing applications. Highly sensitive absorption measurements in the mid-IR may be carried out by Fiber-optic Evanescent Wave Spectroscopy (FEWS). A typical FEWS system is based on three mid-IR components: a tunable source, a detector and a AgClBr fiber sensor that is brought in contact with the samples. We used FTIR spectrometers or tunable gas lasers or quantum cascade lasers (QCLs) as mid-IR sources. We used this FEWS system for measurements on gases, liquids and solids. In particular we used it for several biomedical applications. Measurements in vivo: (1) Early detection of skin diseases (e.g. melanoma). (2) Measurements on cells and bacteria. (3) Measurements on cornea. Measurements in vitro: (4) Characterization of urinary and biliary stones. (5) Blood measurements. The FEWS method is simple, inexpensive and does not require sample processing. It would be useful for diagnostic measurements on the outer part of the body of a patient, as well as for endoscopic measurements. It would also useful for measurements on tissue samples removed from the body. In addition we develop Scanning Near-field Infrared Microscope that will be used for spectral imaging with sub-wavelength resolution in the mid-IR. The various AgClBr fiber-optic sensors are expected to be important diagnostic tools at the hand of physicians in the future.

  8. Design of multilayered grating couplers as key elements of a fully integrated IR-absorption sensor

    NASA Astrophysics Data System (ADS)

    Kasberger, Juergen; Jakoby, Bernhard

    2008-08-01

    For the online characterization of fluids regarding their chemical composition, the miniaturization of an IR-absorption sensor at application-specific distinguished wavelengths for the mid-IR-region promises outstanding features. Utilizing micromachining technology facilitates the integration of all required components (including thermal emitter and detector) into a complete sensor system. The absorption is sensed in the evanescent field of an appropriately designed slab mono-mode waveguide (ZnSe, n=2.42) residing on a BaF2-substrate (n=1.44), which represents the central element of the system. A typical application for such a system is, e.g., the characterization of engine oil oxidation in terms of the absorption at 5.85 μm as an indicator for deterioration. The thermal generation and detection of mid-IR-radiation is preferred over expensive and sophisticated quantum well devices. However, the spatial and non-coherent character of thermally generated IR-radiation requires an extension of the numerical methods established for coherent light sources for a proper design of the system's grating couplers, which act as key elements determining the system performance. These couplers yield efficient coupling into and out of the sensing waveguide and provide the required spectral filtering at the same time. In the actually projected implementation, a multilayer waveguide Si/BaF2/ZnSe is used, where the silicon substrate practically represents a rear-reflector in the grating region featuring several advantages compared to simpler grating couplers. In this contribution we discuss the modelling of the coupling of non-coherent, thermally generated and detected IR-radiation by means of these multilayer grating couplers in the context of a fully integrated IR-absorption sensor system.

  9. Impact and radiation influence on solid hydrocarbon transformation and structuring (by IR-spectroscopy)

    NASA Astrophysics Data System (ADS)

    Kovaleva, O.

    2009-04-01

    Solid hydrocarbons (bitumens)-typical specimens of natural organic minerals-are one of the most essential objects of petroleum geology and at the same time-one of the least investigated objects of organic mineralogy. Moreover they can be treated as admissible analogs of meteorite carbonaceous materials. According to terrestrial analog of meteoritic organic matter it's possible to estimate the chemical structure of extraterrestrial matter. Further investigation of impact force and radiation influence on the bitumen chemical structure change will make it possible to connect them with extraterrestrial organic matter. This work represents the research of impact influence on the processes of transformation and structuring of asphaltite and changes in the molecular structure of solid bitumens constituting the carbonization series (asphaltite--kerite--anthraxolite), which were subjected to the impact of high radiation doses (10 and 100 Mrad) by infrared spectroscopy (IRS). In percussion experiments peak pressure varied from 10 to 63.4 GPa; temperature - from the first tens degrees to several hundreds degrees Celsius. The radiation experiment was performed in the Arzamas-16 Federal Nuclear Center in line with conditions described in [1]. Asphaltite, which sustained shock load from 17.3 to 23 GPa, didn't undergo considerable changes in its element composition. Though their IR-spectra differ from the spectrum of initial asphaltite by heightened intensity of absorption bands of aromatic groups, as well as by insignificant rise of heterogroups and condensed structures oscillation strength. At the same time the intensity of aliphatic (СН2 and СН3) groups absorption hasn't changed. Probably there've just been the carbon and hydrogen atomic rearrangement. However, shock load up to 26.7 GPa leads to asphaltite transformation into the albertite. There've been observed the intensity decrease of aliphatic groups on its IR-spectrum. Under growth of shock load up to 60 GPa bitumen

  10. Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing

    PubMed Central

    Borri, Simone; Siciliani de Cumis, Mario; Insero, Giacomo; Bartalini, Saverio; Cancio Pastor, Pablo; Mazzotti, Davide; Galli, Iacopo; Giusfredi, Giovanni; Santambrogio, Gabriele; Savchenkov, Anatoliy; Eliyahu, Danny; Ilchenko, Vladimir; Akikusa, Naota; Matsko, Andrey; Maleki, Lute; De Natale, Paolo

    2016-01-01

    The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF2 microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line. PMID:26901199

  11. Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing.

    PubMed

    Borri, Simone; Siciliani de Cumis, Mario; Insero, Giacomo; Bartalini, Saverio; Cancio Pastor, Pablo; Mazzotti, Davide; Galli, Iacopo; Giusfredi, Giovanni; Santambrogio, Gabriele; Savchenkov, Anatoliy; Eliyahu, Danny; Ilchenko, Vladimir; Akikusa, Naota; Matsko, Andrey; Maleki, Lute; De Natale, Paolo

    2016-01-01

    The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF₂ microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line. PMID:26901199

  12. ATR-FT-IR spectroscopy in the region of 500-230 cm -1 for identification of inorganic red pigments

    NASA Astrophysics Data System (ADS)

    Vahur, Signe; Knuutinen, Ulla; Leito, Ivo

    2009-08-01

    It is demonstrated that micro-ATR-FT-IR in the low wave number range (500-230 cm -1) can be well used for identification of pigments in paint samples thereby markedly extending the possibilities of pigment identification by ATR-IR spectroscopy into the realm of pigments having no absorptions in the mid-IR region. Reference spectra of pigments can be conveniently obtained by mixing them with linseed oil in approximately 1:1 mass ratio. Vermilion (or cinnabar), read lead, different red iron oxide pigments and cadmium red can be identified. In some cases the method can be used alone for pigment identification and in many cases it provides useful additional evidence for pigment identification using other instrumental techniques (electron microprobe analysis, XRF, optical microscopy).

  13. Determination of methyl radical concentrations in a methane/air flame by infrared cavity ringdown laser absorption spectroscopy

    SciTech Connect

    Scherer, J.J.; Aniolek, K.W.; Cernansky, N.P.; Rakestraw, D.J.

    1997-10-01

    Infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) is employed to determine absolute methyl radical concentrations in a 37.5 Torr laminar methane/air flame. IR-CRLAS rovibrational absorption spectra of the {nu}{sub 3} fundamental band system near 3200thinspcm{sup {minus}1} are combined with N{sub 2}-CARS temperature measurements to obtain methyl radical concentrations as a function of height above the burner surface. These data are compared with flame chemistry simulations under both stoichiometric and rich flame conditions. Issues regarding the applicability of IR-CRLAS for combustion studies are discussed, including the uncertainties present for the specific case of methyl radical. These IR-CRLAS measurements indicate the ability to monitor reactants, intermediates, and products within a narrow spectral window, and, to our knowledge, constitute the first infrared detection of a polyatomic radical in a flame. {copyright} {ital 1997 American Institute of Physics.}

  14. Molecular shock response of explosives: electronic absorption spectroscopy

    SciTech Connect

    Mcgrne, Shawn D; Moore, David S; Whitley, Von H; Bolme, Cindy A; Eakins, Daniel E

    2009-01-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the question of the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference from the shock front as well as broadband increased absorption. Relation to shock initiation hypotheses and the need for time dependent absorption data (future experiments) is briefly discussed.

  15. UV-Vis Reflection-Absorption Spectroscopy at air-liquid interfaces.

    PubMed

    Rubia-Payá, Carlos; de Miguel, Gustavo; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-11-01

    UV-Visible Reflection-Absorption Spectroscopy (UVRAS) technique is reviewed with a general perspective on fundamental and applications. UVRAS is formally identical to IR Reflection-Absorption Spectroscopy (IRRAS), and therefore, the methodology developed for this IR technique can be applied in the UV-visible region. UVRAS can be applied to air-solid, air-liquid or liquid-liquid interfaces. This review focuses on the use of UVRAS for studying Langmuir monolayers. We introduce the theoretical framework for a successful understanding of the UVRAS data, and we illustrate the usage of this data treatment to a previous study from our group comprising an amphiphilic porphyrin. For ultrathin films with a thickness of few nm, UVRAS produces positive or negative bands when p-polarized radiation is used, depending on the incidence angle and the orientation of dipole absorption. UVRAS technique provides highly valuable information on tilt of chromophores at the air-liquid interface, and moreover allows the determination of optical parameters. We propose UVRAS as a powerful technique to investigate the in situ optical properties of Langmuir monolayers. PMID:26385430

  16. Atomic Absorption Spectroscopy. The Present and the Future.

    ERIC Educational Resources Information Center

    Slavin, Walter

    1982-01-01

    The status of current techniques and methods of atomic absorption (AA) spectroscopy (flame, hybrid, and furnace AA) is discussed, including limitations. Technological opportunities and how they may be used in AA are also discussed, focusing on automation, microprocessors, continuum AA, hybrid analyses, and others. (Author/JN)

  17. Visualizing the Solute Vaporization Interference in Flame Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Dockery, Christopher R.; Blew, Michael J.; Goode, Scott R.

    2008-01-01

    Every day, tens of thousands of chemists use analytical atomic spectroscopy in their work, often without knowledge of possible interferences. We present a unique approach to study these interferences by using modern response surface methods to visualize an interference in which aluminum depresses the calcium atomic absorption signal. Calcium…

  18. Laser photothermal spectroscopy of light-induced absorption

    SciTech Connect

    Skvortsov, L A

    2013-01-31

    Basic methods of laser photothermal spectroscopy, which are used to study photoinduced absorption in various media, are briefly considered. Comparative analysis of these methods is performed and the latest results obtained in this field are discussed. Different schemes and examples of their practical implementation are considered. (review)

  19. Absorption and Emission Spectroscopy of a Lasing Material: Ruby

    ERIC Educational Resources Information Center

    Esposti, C. Degli; Bizzocchi, L.

    2007-01-01

    Ruby is a crystalline material, which comes very expensive and is of great significance, as it helped in the creation of first laser. An experiment to determine the absorption and emission spectroscopy, in addition to the determination of the room-temperature lifetime of the substance is being described.

  20. Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Drew, John

    2008-01-01

    In this article I explain why I wrote the set of teaching notes on Atomic Absorption Spectroscopy (AAS) and why they look the way they do. The notes were intended as a student reference to question, highlight and write over as much as they wish during an initial practical demonstration of the threshold concept being introduced, in this case…

  1. FT-IR spectroscopy combined with DFT calculation to explore solvent effects of vinyl acetate.

    PubMed

    Chen, Yi; Zhang, Hui; Liu, Qing

    2014-05-21

    The infrared vibration frequencies of vinyl acetate (VAc) in 18 different solvents were theoretically computed at Density Function Theory (DFT) B3LYP/6-311G(*) level based on Polarizable Continuum Model (PCM) and experimentally recorded by FT-IR spectroscopy. The solvent-induced long-range bulk electrostatic solvation free energies of VAc (ΔGelec) were calculated by the SMD model. The C=O stretching vibration frequencies of VAc were utilized as a measure of the chemical reactivities of the CC group in VAc. The calculated and experimental C=O stretching vibration frequencies of VAc (νcal(C=O) and νexp(C=O)) were correlated with empirical solvent parameters including the KBM equation, the Swain equation and the linear solvation energy relationships (LSER). Through ab initio calculation, assignments of the two C=O absorption bands of VAc in alcohol solvents were achieved. The PCM, SMD and ab initio calculation offered supporting evidence to explain the FT-IR experimental observations from differing aspects. PMID:24607466

  2. Electrochromic poly(acetylene)s with switchable visible/near-IR absorption characteristics.

    PubMed

    Pauly, Anja C; Varnado, C Daniel; Bielawski, Christopher W; Theato, Patrick

    2014-01-01

    Ferrocene is incorporated into a poly(acetylene) derivative via the postpolymerization amidation of a polymer precursor bearing pentafluorophenyl ester-leaving groups with aminoferrocene. While the neutral polymer exhibits a strong absorbance at 553 nm due to its conjugated backbone, oxidation of the ferrocene moieties with silver tetrafluoroborate causes the material to absorb in the near-IR (λ max ≈ 1215 nm). Subsequent reduction of the oxidized polymer with decamethylferrocene restores the initial absorbance profile, demonstrating that the material features switchable visible/near-IR absorption characteristics. PMID:23996218

  3. XANES and IR spectroscopy study of the electronic structure and chemical composition of porous silicon on n- and p-type substrates

    SciTech Connect

    Lenshin, A. S. Kashkarov, V. M.; Seredin, P. V.; Spivak, Yu. M.; Moshnikov, V. A.

    2011-09-15

    The differences in the electronic structure and composition of porous silicon samples obtained under identical conditions of electrochemical etching on the most commonly used n- and p-type substrates with different conductivities are demonstrated by X-ray absorption near-edge spectroscopy (XANES) and Fourier transform IR spectroscopy (FTIR) methods. It is shown that significantly higher oxidation and saturation with hydrogen is observed for the porous layer on n-type substrates.

  4. A combined IR/IR and IR/UV spectroscopy study on the proton transfer coordinate of isolated 3-hydroxychromone in the electronic ground and excited state.

    PubMed

    Stamm, A; Weiler, M; Brächer, A; Schwing, K; Gerhards, M

    2014-10-21

    In this paper the excited state proton transfer (ESPT) of isolated 3-hydroxychromone (3-HC), the prototype of the flavonols, is investigated for the first time by combined IR/UV spectroscopy in molecular beam experiments. The IR/UV investigations are performed both for the electronically excited and electronic ground state indicating a spectral overlap of transitions of the 3-HC monomer and clusters with water in the electronic ground state, whereas in the excited state only the IR frequencies of the proton-transferred monomer structure are observed. Due to the loss of isomer and species selectivity with respect to the UV excitations IR/IR techniques are applied in order to figure out the assignment of the vibrational transitions in the S0 state. In this context the quadruple resonance IR/UV/IR/UV technique (originally developed to distinguish different isomers in the electronically excited state) could be applied to identify the OH stretching vibration of the monomer in the electronic ground state. In agreement with calculations the OH stretching frequency differs significantly from the corresponding values of substituted hydroxychromones. PMID:25200683

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  6. Shaping of broad IR absorption in proton transfer equilibrating OH⋯N hydrogen bonded systems

    NASA Astrophysics Data System (ADS)

    Schreiber, V. M.; Rospenk, M.; Kulbida, A. I.; Sobczyk, L.

    1997-10-01

    The temperature dependence of UV and IR absorption spectra of chlorophenols with tributylamine (TBA) were studied in solution and in low temperature matrices. The UV spectra allowed us to estimate the proton transfer (PT) equilibrium constants and thermodynamic parameters for this process. A strong negative entropy effect was confirmed. In cases when proton transfer species are detected in UV spectrum, a frequency broad absorption below 700 cm -1 usually appears, which we ascribe to non-aggregated species. The potential energy curve for the proton motion is then characterized most probably by a low lying second minimum or a shoulder. The increase of charge separation evoked by aggregation or by enhancement of solvent polarity leads to disappearance of low frequency wing of broad absorption. The involvement of low frequency modes of TBA and phenol moieties, particularly bending δCNC and δNCC modes in shaping of the low frequency part of broad absorption was shown.

  7. Phthalocyanine adsorption to graphene on Ir(111): Evidence for decoupling from vibrational spectroscopy

    SciTech Connect

    Endlich, M. Gozdzik, S.; Néel, N.; Kröger, J.; Rosa, A. L. da; Frauenheim, T.; Wehling, T. O.

    2014-11-14

    Phthalocyanine molecules have been adsorbed to Ir(111) and to graphene on Ir(111). From a comparison of scanning tunneling microscopy images of individual molecules adsorbed to the different surfaces alone it is difficult to discern potential differences in the molecular adsorption geometry. In contrast, vibrational spectroscopy using inelastic electron scattering unequivocally hints at strong molecule deformations on Ir(111) and at a planar adsorption geometry on graphene. The spectroscopic evidence for the different adsorption configurations is supported by density functional calculations.

  8. Multiwavelength diode-laser absorption spectroscopy using external intensity modulation by semiconductor optical amplifiers.

    PubMed

    Karagiannopoulos, Solon; Cheadle, Edward; Wright, Paul; Tsekenis, Stylianos; McCann, Hugh

    2012-12-01

    A novel opto-electronic scheme for line-of-sight Near-IR gas absorption measurement based on direct absorption spectroscopy (DAS) is reported. A diode-laser-based, multiwavelength system is designed for future application in nonintrusive, high temporal resolution tomographic imaging of H2O in internal combustion engines. DAS is implemented with semiconductor optical amplifiers (SOAs) to enable wavelength multiplexing and to induce external intensity modulation for phase-sensitive detection. Two overtone water transitions in the Near-IR have been selected for ratiometric temperature compensation to enable concentration measurements, and an additional wavelength is used to account for nonabsorbing attenuation. A wavelength scanning approach was used to evaluate the new modulation technique, and showed excellent absorption line recovery. Fixed-wavelength, time-division-multiplexing operation with SOAs has also been demonstrated. To the best of our knowledge this is the first time SOAs have been used for modulation and switching in a spectroscopic application. With appropriate diode laser selection this scheme can be also used for other chemical species absorption measurements. PMID:23207374

  9. Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation

    NASA Astrophysics Data System (ADS)

    Drescher, L.; Galbraith, M. C. E.; Reitsma, G.; Dura, J.; Zhavoronkov, N.; Patchkovskii, S.; Vrakking, M. J. J.; Mikosch, J.

    2016-07-01

    Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π → σ* excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.

  10. Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation.

    PubMed

    Drescher, L; Galbraith, M C E; Reitsma, G; Dura, J; Zhavoronkov, N; Patchkovskii, S; Vrakking, M J J; Mikosch, J

    2016-07-01

    Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π → σ(*) excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings. PMID:27394091

  11. Human epithelial cancer cells studied using combined AFM-IR absorption nanoimaging

    NASA Astrophysics Data System (ADS)

    Kennedy, Eamonn; Al-Majomaie, Rasoul; Zerulla, Dominic; Al-Rubeai, Mohammed; Rice, James H.

    2014-05-01

    Several recent studies have described the use of infrared (IR) nanoimaging for non-invasive chemical discrimination of subcellular features and intracellular exogenous agents. In this work we outline a number of improvements in both quantitative IR nanoimage analysis and optical system improvements which enable recovery of nanoscale subcellular chemical localization with improved chemical precision. Additionally, we demonstrate how a combination of IR absorption nanoimaging and topographic data can produce subcellular chemical density and complexity maps, which can illustrate several cellular features of interest, including the label free localization of nuclei for both healthy and cancerous cell lines with sub 40nm accuracy. As many cell processes related to disease are governed by the position and dynamics of subcellular features, we present the ability to map biochemical inhomogeneity of cancer cells at nanoscale resolution as a means to explore the subcellular biomechanics underlying carcinogenesis.

  12. Light-induced changes in subband absorption in a-Si:H using photoluminescence absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gu, S. Q.; Taylor, P. C.; Nitta, S.

    1991-08-01

    We have used the photoluminescence (PL) generated in a thin-film sample of a-Si:H to probe low absorption levels by measuring the absorption of the PL as it travels down the length of the film in a waveguide mode. This technique, which we have called PL absorption spectroscopy of PLAS, allows the measurement of values of the absorption coefficient α down to about 0.1 cm-1. Because this technique probes the top and bottom surfaces of the a-Si:H sample, it is important to separate surface from bulk absorption mechanisms. An improved sample geometry has been employed to facilitate this separation. One sample consisted of an a-Si1-xNix:H/a-Si:H/ a-Si1-xNx:H/NiCr layered structure where the silicon nitride layers served as the cladding layers for the waveguide. In a second sample the a-Si:H layer was interrupted near the middle for two separate, thin (100 Å) layers of a-Si1-xNx:H in order to check for the importance of the absorption at the silicon/silicon nitride interfaces in these PLAS measurements. Changes in the below-gap absorption on light soaking were examined using irradiation from an Ar+ laser (5145 Å, ˜200 mW/cm2 for 5.5 hours at 300 K). The silicon/silicon nitride interface is responsible for an absorption which has a shoulder near 1.2 eV while the bulk a-Si:H absorption exhibits no such shoulder. The metastable, optically-induced increase in the below gap absorption appears to come entirely from the bulk of the a-Si:H. These low temperature PLAS measurements are compared with those obtained at 300 K by photothermal deflection spectroscopy.

  13. IR and IR + UV spectroscopy of isolated [Al-AcPheOMe]n+ cluster cations (n = 1, 3).

    PubMed

    Bialach, P M; Martin, T C; Gerhards, M

    2012-06-14

    Singly and triply charged cationic clusters of aluminium and the protected amino acid AcPheOMe are investigated in a supersonic beam by using a combination of a thermic and a laser ablation ion source. For the singly charged species UV- and IR photodissociation spectroscopy is applied. In the case of the triply charged clusters a variant of combined IR + UV spectroscopy is used to obtain information in the NH-stretching region. By comparison with DFT calculations structural assignments are suggested and it turns out that both clusters prefer a helical arrangement with aluminium being aggregated to both carbonyl groups. For the triply charged cluster a globular structure is formed in which aluminium is captured both by the carbonyl groups and the phenyl ring. PMID:22532114

  14. FT-IR spectroscopy characterization of schwannoma: a case study

    NASA Astrophysics Data System (ADS)

    Ferreira, Isabelle; Neto, Lazaro P. M.; das Chagas, Maurilio José; Carvalho, Luís. Felipe C. S.; dos Santos, Laurita; Ribas, Marcelo; Loddi, Vinicius; Martin, Airton A.

    2016-03-01

    Schwannoma are rare benign neural neoplasia. The clinical diagnosis could be improved if novel optical techniques are performed. Among these techniques, FT-IR is one of the currently techniques which has been applied for samples discrimination using biochemical information with minimum sample preparation. In this work, we report a case of a schwannoma in the cervical region. A histological examination described a benign process. An immunohistochemically examination demonstrated positivity to anti-S100 protein antibody, indicating a diagnosis of schwannoma. The aim of this analysis was to characterize FT-IR spectrum of the neoplastic and normal tissue in the fingerprint (1000-1800 cm-1) and high wavenumber region (2800-3600 cm-1). The IR spectra were collect from tumor tissue and normal nerve samples by a FT-IR spectrophotometer (Spotlight Perkin Elmer 400, USA) with 64 scans, and resolution of 4 cm-1. A total of twenty spectra were recorded (10 from schwannoma and 10 from nerve). Multivariate Analysis was used to classify the data. Through average and standard deviation analysis we observed that the main spectral change occurs at ≍1600 cm-1 (amide I) and ≍1400 cm-1 (amide III) in the fingerprint region, and in CH2/CH3 protein-lipids and OH-water vibrations for the high wavenumber region. In conclusion, FT-IR could be used as a technique for schwannoma analysis helping to establish specific diagnostic.

  15. Rapid discrimination of extracts of Chinese propolis and poplar buds by FT-IR and 2D IR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Yan-Wen; Sun, Su-Qin; Zhao, Jing; Li, Yi; Zhou, Qun

    2008-07-01

    The extract of Chinese propolis (ECP) has recently been adulterated with that of poplar buds (EPB), because most of ECP is derived from the poplar plant, and ECP and EPB have almost identical chemical compositions. It is very difficult to differentiate them by using the chromatographic methods such as high performance liquid chromatography (HPLC) and gas chromatography (GC). Therefore, how to effectively discriminate these two mixtures is a problem to be solved urgently. In this paper, a rapid method for discriminating ECP and EPB was established by the Fourier transform infrared (FT-IR) spectra combined with the two-dimensional infrared correlation (2D IR) analysis. Forty-three ECP and five EPB samples collected from different areas of China were analyzed by the FT-IR spectroscopy. All the ECP and EPB samples tested show similar IR spectral profiles. The significant differences between ECP and EPB appear in the region of 3000-2800 cm -1 of the spectra. Based on such differences, the two species were successfully classified with the soft independent modeling of class analogy (SIMCA) pattern recognition technique. Furthermore, these differences were well validated by a series of temperature-dependent dynamic FT-IR spectra and the corresponding 2D IR plots. The results indicate that the differences in these two natural products are caused by the amounts of long-chain alkyl compounds (including long-chain alkanes, long-chain alkyl esters and long chain alkyl alcohols) in them, rather than the flavonoid compounds, generally recognized as the bioactive substances of propolis. There are much more long-chain alkyl compounds in ECP than those in EPB, and the carbon atoms of the compounds in ECP remain in an order Z-shaped array, but those in EPB are disorder. It suggests that FT-IR and 2D IR spectroscopy can provide a valuable method for the rapid differentiation of similar natural products, ECP and EPB. The IR spectra could directly reflect the integrated chemical

  16. Impact and radiation influence on solid hydrocarbon transformation and structuring (by IR-spectroscopy)

    NASA Astrophysics Data System (ADS)

    Kovaleva, O.

    2009-04-01

    Solid hydrocarbons (bitumens)-typical specimens of natural organic minerals-are one of the most essential objects of petroleum geology and at the same time-one of the least investigated objects of organic mineralogy. Moreover they can be treated as admissible analogs of meteorite carbonaceous materials. According to terrestrial analog of meteoritic organic matter it's possible to estimate the chemical structure of extraterrestrial matter. Further investigation of impact force and radiation influence on the bitumen chemical structure change will make it possible to connect them with extraterrestrial organic matter. This work represents the research of impact influence on the processes of transformation and structuring of asphaltite and changes in the molecular structure of solid bitumens constituting the carbonization series (asphaltite--kerite--anthraxolite), which were subjected to the impact of high radiation doses (10 and 100 Mrad) by infrared spectroscopy (IRS). In percussion experiments peak pressure varied from 10 to 63.4 GPa; temperature - from the first tens degrees to several hundreds degrees Celsius. The radiation experiment was performed in the Arzamas-16 Federal Nuclear Center in line with conditions described in [1]. Asphaltite, which sustained shock load from 17.3 to 23 GPa, didn't undergo considerable changes in its element composition. Though their IR-spectra differ from the spectrum of initial asphaltite by heightened intensity of absorption bands of aromatic groups, as well as by insignificant rise of heterogroups and condensed structures oscillation strength. At the same time the intensity of aliphatic (СН2 and СН3) groups absorption hasn't changed. Probably there've just been the carbon and hydrogen atomic rearrangement. However, shock load up to 26.7 GPa leads to asphaltite transformation into the albertite. There've been observed the intensity decrease of aliphatic groups on its IR-spectrum. Under growth of shock load up to 60 GPa bitumen

  17. Probing Heat Transfer Through Infrared (IR), Near-IR, and Visible Spectroscopy of Lattice Modes, Overtones, Hydrogen Species, and Electronic Transitions

    NASA Astrophysics Data System (ADS)

    Hofmeister, A. M.

    2006-05-01

    Thermal conductivity (k, or its close relative, thermal diffusivity D = k/density.heat capacity) governs the flow of heat in minerals and high pressure phases. Quantifying the dependence of k on temperature, pressure, composition and phase is important because these variations largely control mantle convection, and dictate lithospheric conduction. One component (klat) arises from the microscopic phenomena of vibrations, as recognized by Debye and Einstein. Not only are absolute values of klat grossly uncertain, due to contact losses of heat, but systematic errors exist in the temperature derivatives due to contact plus unwanted, direct radiative transfer. Due to inaccuracies in k data, problems in acoustic models are under-recognized. Recent advances in engineering provide accurate measurements of minerals via the laser-flash technique (specifically radiative transfer effects and contact are eliminated in this IR method). New laser-flash data gathered in our laboratory on D(T) of olivine, garnet, spinel, quartz and other minerals are best described by the optic model based on damped harmonic analysis of quantitative IR and Raman spectra (Hofmeister 2001 Am Min; 2006 PCM), not by acoustic models. Theoretical considerations, and comparing spectroscopic and heat transport measurements shows that 1/D is closely related to heat capacity, which is controlled by optic modes above room T. As a consequence, D and klat asymptote to constants at high T, and values inside Earth are governed by pressure behavior. Accurate measurement of klat and D are limited to low pressure, and thus spectroscopy at high pressure in conjunction with optic models are essential to provide mantle values. The optic model could be made even more robust if vibrational spectra studies at T and P examined peak widths as well as peak positions. Inside Earth, heat is transported diffusively by radiative transfer (kPrad,dif). This process involves sequential emission, absorption and reemission of light

  18. Infrared absorption spectroscopy and chemical kinetics of free radicals

    SciTech Connect

    Curl, R.F.; Glass, G.P.

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  19. Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

    PubMed

    Kao, Joseph P Y; Muralidharan, Sukumaran

    2013-01-01

    Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter. PMID:23494372

  20. Determination of Dihydrobenzoacridinone Structures by NMR, IR, and UV Spectroscopy and Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Kozlov, N. G.; Zhiharko, Yu. D.; Skakovsky, E. D.; Baranovsky, A. V.; Ogorodnikova, M. M.; Basalaeva, L. I.

    2016-01-01

    Condensation of 2-naphthylamine, aromatic aldehydes, and dimedone was found to produce 9,10-dihydrobenzo[a] acridin-11-one derivatives according to PMR, 13C NMR, and IR spectroscopy and mass spectrometry. Correlation spectroscopy showed that the carbonyl in the synthesized dihydrobenzoacridinone derivatives was located on C11.

  1. Total absorption spectroscopy of the β decay of 76Ga

    NASA Astrophysics Data System (ADS)

    Dombos, A. C.; Fang, D.-L.; Spyrou, A.; Quinn, S. J.; Simon, A.; Brown, B. A.; Cooper, K.; Gehring, A. E.; Liddick, S. N.; Morrissey, D. J.; Naqvi, F.; Sumithrarachchi, C. S.; Zegers, R. G. T.

    2016-06-01

    The β decay of 76Ga was studied using the technique of total absorption spectroscopy for the first time. The experiment was performed at the National Superconducting Cyclotron Laboratory using the Summing NaI(Tl) detector. The extracted β -decay feeding intensity distribution and Gamow-Teller transition strength distribution are compared to shell-model calculations to help constrain nuclear matrix elements relevant to the neutrinoless double-β decay of 76Ge.

  2. Label free detection of phospholipids by infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahmed, Tahsin; Foster, Erick; Vigil, Genevieve; Khan, Aamir A.; Bohn, Paul; Howard, Scott S.

    2014-08-01

    We present our study on compact, label-free dissolved lipid sensing by combining capillary electrophoresis separation in a PDMS microfluidic chip online with mid-infrared (MIR) absorption spectroscopy for biomarker detection. On-chip capillary electrophoresis is used to separate the biomarkers without introducing any extrinsic contrast agent, which reduces both cost and complexity. The label free biomarker detection could be done by interrogating separated biomarkers in the channel by MIR absorption spectroscopy. Phospholipids biomarkers of degenerative neurological, kidney, and bone diseases are detectable using this label free technique. These phospholipids exhibit strong absorption resonances in the MIR and are present in biofluids including urine, blood plasma, and cerebrospinal fluid. MIR spectroscopy of a 12-carbon chain phosphatidic acid (PA) (1,2-dilauroyl-snglycero- 3-phosphate (sodium salt)) dissolved in N-methylformamide, exhibits a strong amide peak near wavenumber 1660 cm-1 (wavelength 6 μm), arising from the phosphate headgroup vibrations within a low-loss window of the solvent. PA has a similar structure to many important phospholipids molecules like phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and phosphatidylserine (PS), making it an ideal molecule for initial proof-of-concept studies. This newly proposed detection technique can lead us to minimal sample preparation and is capable of identifying several biomarkers from the same sample simultaneously.

  3. Reduced-background gas-phase absorption spectroscopy.

    PubMed

    Sweetser, J N; Trebino, R

    1998-08-15

    We propose and demonstrate a new method for single-shot multiplex absorption spectroscopy that permits enhanced sensitivity in the simultaneous measurement of multiple spectral lines in rapidly changing gas-phase media, such as turbulent flames. It uses an ultrashort laser pulse that propagates through the absorbing medium, for which the relevant absorption information resides in the free-induction decay that is trailing behind the transmitted pulse. Time gating out most of the transmitted pulse, but not the free-induction decay, enhances the relative fraction of light that contains absorption information when the spectrum is measured. This procedure reduces the background associated with the input light, thus enhancing detection sensitivity. PMID:18087501

  4. Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice. I. Mid-IR spectroscopy and photoproducts

    NASA Astrophysics Data System (ADS)

    Bouwman, J.; Mattioda, A. L.; Linnartz, H.; Allamandola, L. J.

    2011-01-01

    Context. Polycyclic aromatic hydrocarbons (PAHs) are known to be abundantly present in photon-dominated regions (PDRs), as evidenced by their ubiquitous mid-IR emission bands. Towards dense clouds, however, their IR emission bands are strongly suppressed. It is here where molecules are known to reside on very cold grains (T ≤ 30 K) in the form of interstellar ices. Therefore, it is likely that non-volatile species, such as PAHs, also freeze out on grains. Such icy grains act as catalytic sites and, upon vacuum ultraviolet (VUV) irradiation, chemical reactions are initiated. In the study presented here, these reactions and the resulting photoproducts are investigated for PAH containing water ices. Aims: The aim of this work is to monitor vacuum ultraviolet induced chemical reactions of PAHs in cosmic ice through their IR signatures, to characterize the families of species formed in these reactions, and to apply the results to astronomical observations. Methods: Mid-infrared Fourier transform absorption spectroscopic measurements ranging from 6500 to 450 cm-1 are performed on freshly deposited and vacuum ultraviolet processed PAH containing cosmic H2O ices at low temperatures. Results: The mid-IR spectroscopy of anthracene, pyrene and benzo[ghi]perylene containing H2O ice is reported. Band strengths of the neutral PAH modes in H2O ice are derived. Additionally, spectra of vacuum ultraviolet processed PAH containing H2O ices are presented. These spectra are compared to spectra measured in VUV processed PAH:argon matrix isolation studies. It is concluded that the parent PAH species is ionized in H2O ice and that other photoproducts, mainly more complex PAH derivatives, also form. The importance of PAHs and their PAH:H2O photoproducts in astronomical mid-infrared spectroscopic studies, in particular in the 5-8 μm region, is discussed. As a test-case, the VUV photolyzed PAH:H2O laboratory spectra are compared to a high resolution ISO-SWS spectrum of the high

  5. Time-Resolved X-Ray Absorption Spectroscopy Data for the Study of Chemical Reaction Intermediate States

    SciTech Connect

    Diaz Moreno, Sofia; Bowron, Daniel T.; Evans, John

    2007-02-02

    Energy-dispersive X-ray absorption Spectroscopy is an increasingly powerful tool for the investigation of kinetic processes in chemical systems as an element-specific local structure and electronic-state probe. In this paper we present a study of the structural evolution of the inner-sphere electron transfer reaction between [IrCl6]2- and [Co(CN)5]3-. The experimental requirements necessary for the extraction of maximal structural and electronic information are discussed.

  6. FT-IR spectroscopy of lipoproteins—A comparative study

    NASA Astrophysics Data System (ADS)

    Krilov, Dubravka; Balarin, Maja; Kosović, Marin; Gamulin, Ozren; Brnjas-Kraljević, Jasminka

    2009-08-01

    FT-IR spectra, in the frequency region 4000-600 cm -1, of four major lipoprotein classes: very low density lipoprotein (VLDL), low density lipoprotein (LDL) and two subclasses of high density lipoproteins (HDL 2 and HDL 3) were analyzed to obtain their detailed spectral characterization. Information about the protein domain of particle was obtained from the analysis of amide I band. The procedure of decomposition and curve fitting of this band confirms the data already known about the secondary structure of two different apolipoproteins: apo A-I in HDL 2 and HDL 3 and apo B-100 in LDL and VLDL. For information about the lipid composition and packing of the particular lipoprotein the well expressed lipid bands in the spectra were analyzed. Characterization of spectral details in the FT-IR spectrum of natural lipoprotein is necessary to study the influence of external compounds on its structure.

  7. Ultradeep Spitzer IRS Spectroscopy in the GOODS Southern Field

    NASA Astrophysics Data System (ADS)

    Teplitz, H. I.; Armus, L.; Chary, R.; Colbert, J. W.; Frayer, D.; Desai, V.; Blain, A.; Spoon, H.; Charmandaris, V.; Pope, A.; Scott, D.

    2005-12-01

    We present the deepest spectra taken to date by the Infrared Spectrometer (IRS) on the Spitzer Space Telescope. We targeted two faint ( ˜ 0.15 mJy) sources in the Southern GOODS field, at z=1.09 and z=2.69, as likely star-forming galaxies. Spectra of the lower redshift target were taken in 8-21 micron range (short-low first order and long-low second order), while the higher redshift target was observed from 21-37 microns (long-low first order). Observing times were 3 and 9 hours on-source for SL-1 and LL-2, respectively, and 12 hours for LL-1. We detect strong PAH emission in both targets. We compare the spectra to those of local galaxies observed by the IRS.

  8. Secondary structure of proteins analyzed ex vivo in vascular wall in diabetic animals using FT-IR spectroscopy.

    PubMed

    Majzner, Katarzyna; Wrobel, Tomasz P; Fedorowicz, Andrzej; Chlopicki, Stefan; Baranska, Malgorzata

    2013-11-12

    In recent years many methods for ex vivo tissue analysis or diagnosis of diseases have been applied, including infrared absorption spectroscopy. Fourier-transform infrared (FT-IR) absorption microspectroscopy allows the simultaneous monitoring of the content of various chemical compounds in tissues with both high selectivity and resolution. Imaging of tissue samples in very short time can be performed using a spectrometer equipped with a Focal Plane Array (FPA) detector. Additionally, a detection of minor components or subtle changes associated with the functional status of a tissue sample is possible when advanced methods of data analysis, such as chemometric techniques, are applied. Monitoring of secondary structures of proteins has already proved to be useful in the analysis of animal tissues in disease states. The aim of this work was to build a mathematical model based on FT-IR measurements for the prediction of alterations in the content of secondary structures of proteins analyzed by FT-IR in the vascular wall of diabetic animals. For that purpose a spectral database of proteins of known crystallography and secondary structures was assembled. Thirty-seven proteins were measured by means of two FT-IR techniques: transflection and Attenuated Total Reflectance (ATR). The obtained model was tested on cross-sections of rat tail, for which the content of proteins and their secondary structures was well characterized. Then, the model was applied for the detection of possible alterations in the secondary structures of proteins in the vascular wall of diabetic rats and mice. The obtained results suggest a prominent increase in E- and S-structures and a decrease in the content of H-structures in the vascular wall from diabetic mice and rats. FT-IR-based studies of secondary structures of proteins may be a novel approach to study complex processes ongoing in the vascular wall. The obtained results are satisfactory; however, the existing limitations of the method are

  9. Ir-Spectroscopy of Glycine and its Complexes with Water in Helium Nanodroplets

    NASA Astrophysics Data System (ADS)

    Letzner, M.; Grün, S. A.; Schwaab, G.; Havenith, M.

    2011-06-01

    Glycine is the smallest amino acid, and therefore it is of special interest as a model and starting point for theoretical and experimental studies. Whereas the crystalline form of glycine consists of zwitterions NH_3+-CH_2-COO-, gas phase glycine is known to exist in the nonionized form NH_2-CH_2-COOH. The interaction between glycine and water has been widely studied using a large variety of theoretical methods. Depending on the theoretical level used, a stabilisation of the zwitterionic form is predicted for complexes containing from 2 to 7 water molecules. In low-temperature Ar matrices a set of characteristic IR absorption bands for the zwitterionic form has been observed. The higher stoichiometry complexes (glycine)\\cdots(H_2O)_n with n larger than 3 are demonstrated to be zwitterionic H-bonded complexes. The multitude of conformations expected for these glycine-water complexes makes a combination of low temperature and high resolution spectroscopy essential. We want to use the advantages of our experiment to investigate glycine and its complexes with water in helium-nanodroplets at ultracold temperatures in the range from 3000-3800 Cm-1. Our measurements were carried out using a high power IR-OPO (cw: 2.7 W) as radiation source and a helium nanodroplet spectrometer. Helium-nanodroplets are formed by expansion of helium at 55 bar through a 5 μm nozzle which is kept at a temperature of 16 K. The status of the project is presented. P.-G. Jönsson et al., Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 28, 1827 (1972) G. Junk et al., J. Am. Chem. Soc. 85, 839 (1963) R. Ramaekers et al., J. Chem. Phys., 120 (2004)

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

    NASA Astrophysics Data System (ADS)

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

    2000-10-01

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

  11. Far-field infrared super-resolution microscopy using picosecond time-resolved transient fluorescence detected IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakai, Makoto; Kawashima, Yasutake; Takeda, Akihiro; Ohmori, Tsutomu; Fujii, Masaaki

    2007-05-01

    A new far-field infrared super-resolution microscopy combining laser fluorescence microscope and picosecond time-resolved transient fluorescence detected IR (TFD-IR) spectroscopy is proposed. TFD-IR spectroscopy is a kind of IR-visible/UV double resonance spectroscopy, and detects IR transitions by the transient fluorescence due to electronic transition originating from vibrationally excited level populated by IR light. IR images of rhodamine-6G solution and of fluorescent beads were clearly observed by monitoring the transient fluorescence. Super-resolution twice higher than the diffraction limit for IR light was achieved. The IR spectrum due to the transient fluorescence was also measured from spatial domains smaller than the diffraction limit.

  12. Determination of Ethanol in Gasoline by FT-IR Spectroscopy

    ERIC Educational Resources Information Center

    Conklin, Alfred, Jr.; Goldcamp, Michael J.; Barrett, Jacob

    2014-01-01

    Ethanol is the primary oxygenate in gasoline in the United States. Gasoline containing various percentages of ethanol is readily available in the market place. A laboratory experiment has been developed in which the percentage of ethanol in hexanes can easily be determined using the O-H and alkane C-H absorptions in an infrared spectrum. Standard…

  13. Conformations of 1-heptene secondary ozonide as studied by low temperature FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Bariseviciute, R.; Ceponkus, J.; Sablinskas, V.; Kimtys, L.

    2007-11-01

    Conformational diversity of the 1-heptene secondary ozonides (SOZ) in solid neat films as well as isolated in Ar or CO 2 matrices was studied by the means of FT-IR absorption spectroscopy. The ozonization reaction was performed at 77 K in the neat films of the reactants. The spectra of the ozonide were analyzed by combining the experimental data with the results of theoretical calculations performed at B3LYP 6-311++G (3df, 3pd) level. It was found that the samples of 1-heptene secondary ozonide exist as a mixture of three dominating conformers. The most stable conformer is the one with O-O half-chair configuration of the five membered ring, the aliphatic radical attached to the ring in equatorial position and the aliphatic chain being in gauche (∠OCCC ≈ -60°) position. The other two stable conformers are equatorial with aliphatic chain in anti (∠OCCC ≈ 180°) and gauche (∠OCCC ≈ 60°) positions. It was found from Van't Hoff plots that Δ H of the equatorial anti conformer is equal to 0.24 ± 0.03 kJ/mol. The experimental value of Δ H is in reasonable accordance to the calculated one - 0.5 kJ/mol.

  14. Structural dynamics of membrane proteins - time-resolved and surface-enhanced IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Heberle, Joachim

    2013-03-01

    Membrane proteins are the target of more than 50% of all drugs and are encoded by about 30% of the human genome. Electrophysiological techniques, like patch-clamp, unravelled many functional aspects of membrane proteins but suffer from structural sensitivity. We have developed Surface Enhanced Infrared Difference Absorption Spectroscopy (SEIDAS) to probe potential-induced structural changes of a protein on the level of a monolayer. A novel concept is introduced to incorporate membrane proteins into solid supported lipid bilayers in an orientated manner via the affinity of the His-tag to the Ni-NTA terminated gold surface. General applicability of the methodological approach is shown by tethering photosystem II to the gold surface. In conjunction with hydrogenase, the basis is set towards a biomimetic system for hydrogen production. Recently, we succeeded to record IR difference spectra of a monolayer of sensory rhodopsin II under voltage-clamp conditions. This approach opens an avenue towards mechanistic studies of voltage-gated ion channels with unprecedented structural and temporal sensitivity. Initial vibrational studies on the novel light-gated channelrhodopsin-2 (ChR2) will be presented. ChR2 represents a versatile tool in the new field of optogenetics where physiological reactions are controlled by light.

  15. Acoustic levitation as an IR spectroscopy sampling technique

    SciTech Connect

    Cronin, J. T.; Brill, T. B.

    1989-02-01

    Acoustic levitation of liquid droplets (/lt/4 mm diameter), bubbles,and solid particles is described as an unusual sampling techniquefor obtaining the infrared spectrum of samples that might be incompatiblewith conventional sample support methods, and for studies of materialsunder extreme conditions. Excellent FT-IR spectra were recorded ofbubbles of a concentrated aqueous nitrate solution, of mineral oil,and of an aqueous surfactant solution. Polymethacrylic acidpacking foam also produced a high-quality spectrum. Large aqueousdroplets and dense solids gave unsatisfactory spectra. The designof the levitator and various spectroscopic considerations are discussed.

  16. Biochemical applications of surface-enhanced infrared absorption spectroscopy

    PubMed Central

    Heberle, Joachim

    2007-01-01

    An overview is presented on the application of surface-enhanced infrared absorption (SEIRA) spectroscopy to biochemical problems. Use of SEIRA results in high surface sensitivity by enhancing the signal of the adsorbed molecule by approximately two orders of magnitude and has the potential to enable new studies, from fundamental aspects to applied sciences. This report surveys studies of DNA and nucleic acid adsorption to gold surfaces, development of immunoassays, electron transfer between metal electrodes and proteins, and protein–protein interactions. Because signal enhancement in SEIRA uses surface properties of the nano-structured metal, the biomaterial must be tethered to the metal without hampering its functionality. Because many biochemical reactions proceed vectorially, their functionality depends on proper orientation of the biomaterial. Thus, surface-modification techniques are addressed that enable control of the proper orientation of proteins on the metal surface. Figure Surface enhanced infrared absorption spectroscopy (SEIRAS) on the studies of tethered protein monolayer (cytochrome c oxidase and cytochrome c) on gold substrate (left), and its potential induced surface enhanced infrared difference absorption (SEIDA) spectrum PMID:17242890

  17. APPLICATION OF ABSORPTION SPECTROSCOPY TO ACTINIDE PROCESS ANALYSIS AND MONITORING

    SciTech Connect

    Lascola, R.; Sharma, V.

    2010-06-03

    The characteristic strong colors of aqueous actinide solutions form the basis of analytical techniques for actinides based on absorption spectroscopy. Colorimetric measurements of samples from processing activities have been used for at least half a century. This seemingly mature technology has been recently revitalized by developments in chemometric data analysis. Where reliable measurements could formerly only be obtained under well-defined conditions, modern methods are robust with respect to variations in acidity, concentration of complexants and spectral interferents, and temperature. This paper describes two examples of the use of process absorption spectroscopy for Pu analysis at the Savannah River Site, in Aiken, SC. In one example, custom optical filters allow accurate colorimetric measurements of Pu in a stream with rapid nitric acid variation. The second example demonstrates simultaneous measurement of Pu and U by chemometric treatment of absorption spectra. The paper concludes with a description of the use of these analyzers to supplement existing technologies in nuclear materials monitoring in processing, reprocessing, and storage facilities.

  18. Pathlength determination for gas in scattering media absorption spectroscopy.

    PubMed

    Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

    2014-01-01

    Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

  19. Pathlength Determination for Gas in Scattering Media Absorption Spectroscopy

    PubMed Central

    Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

    2014-01-01

    Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

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

    NASA Astrophysics Data System (ADS)

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

    2007-01-01

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

  1. Study on the elemental mercury absorption cross section based on differential optical absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zheng, Haiming; Yao, Penghui

    2015-08-01

    With the method of ultraviolet absorption spectrum, the exact absorption cross-section with the light source of the low-pressure mercury lamp was determined, during which the optimum wavelength for mercury concentrations inversion was 253.69 nm, the highest detection limit was 0.177 μg/cm3, and the lowest detection limit was 0.034 μg/cm3. Furthermore, based on the differential optical absorption spectroscopy(DOAS), the relationship between the integral parameters (IP) and the concentration as well as the signal-noise ration (SNR) under the conditions of gas flow was determined and the lowest detection limit was figured out to be 0.03524 μg/cm3, providing a method of DOAS to de-noise through the comparison between the mercury concentration values produced by DOAS and that produced by the wavelet de-noising method (db5). It turned out that the differential optical absorption spectroscopy had a strong anti-interference ability, while the wavelet de-noising method was not suitable for measuring the trace concentration change.

  2. Study on Angelica and its different extracts by Fourier transform infrared spectroscopy and two-dimensional correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Hong-xia; Sun, Su-qin; Lv, Guang-hua; Chan, Kelvin K. C.

    2006-05-01

    In order to develop a rapid and effective analysis method for studying integrally the main constituents in the medicinal materials and their extracts, discriminating the extracts from different extraction process, comparing the categories of chemical constituents in the different extracts and monitoring the qualities of medicinal materials, we applied Fourier transform infrared spectroscopy (FT-IR) associated with second derivative infrared spectroscopy and two-dimensional correlation infrared spectroscopy (2D-IR) to study the main constituents in traditional Chinese medicine Angelica and its different extracts (extracted by petroleum ether, ethanol and water in turn). The findings indicated that FT-IR spectrum can provide many holistic variation rules of chemical constituents. Use of the macroscopical fingerprint characters of FT-IR and 2D-IR spectrum can not only identify the main chemical constituents in medicinal materials and their different extracts, but also compare the components differences among the similar samples. This analytical method is highly rapid, effective, visual and accurate for pharmaceutical research.

  3. VLT near- to mid-IR imaging and spectroscopy of the M 17 UC1 - IRS5 region

    NASA Astrophysics Data System (ADS)

    Chen, Zhiwei; Nürnberger, Dieter E. A.; Chini, Rolf; Jiang, Zhibo; Fang, Min

    2015-06-01

    Aims: We investigate the surroundings of the hypercompact H ii region M 17 UC1 to probe the physical properties of the associated young stellar objects and the environment of massive star formation. Methods: We use diffraction-limited near-IR (VLT/NACO) and mid-IR (VLT/VISIR) images to reveal the different morphologies at various wavelengths. Likewise, we investigate the stellar and nebular content of the region with VLT/SINFONI integral field spectroscopy with a resolution R ˜ 1500 at H + K bands. Results: Five of the seven point sources in this region show L-band excess emission. A geometric match is found between the H2 emission and near-IR polarized light in the vicinity of IRS5A, and between the diffuse mid-IR emission and near-IR polarization north of UC1. The H2 emission is typical for dense photodissociation regions (PDRs), which are initially far-ultraviolet pumped and repopulated by collisional de-excitation. The spectral types of IRS5A and B273A are B3-B7 V/III and G4-G5 III, respectively. The observed infrared luminosity LIR in the range 1-20 μm is derived for three objects; we obtain 2.0 × 103 L⊙ for IRS5A, 13 L⊙ for IRS5C, and 10 L⊙ for B273A. Conclusions: IRS5 might be a young quadruple system. Its primary star IRS5A is confirmed to be a high-mass protostellar object (˜9 M⊙, ˜1 × 105 yrs); it might have terminated accretion due to the feedback from stellar activities (radiation pressure, outflow) and the expanding H ii region of M 17. The object UC1 might also have terminated accretion because of the expanding hypercompact H ii region, which it ionizes. The disk clearing process of the low-mass young stellar objects in this region might be accelerated by the expanding H ii region. The outflows driven by UC1 are running south-north with its northeastern side suppressed by the expanding ionization front of M 17; the blue-shifted outflow lobe of IRS5A is seen in two types of tracers along the same line of sight in the form of H2 emission

  4. High Resolution FIR and IR Spectroscopy of Methanol Isotopologues

    SciTech Connect

    Lees, R. M.; Xu, Li-Hong; Appadoo, D. R. T.; Billinghurst, B.

    2010-02-03

    New astronomical facilities such as HIFI on the Herschel Space Observatory, the SOFIA airborne IR telescope and the ALMA sub-mm telescope array will yield spectra from interstellar and protostellar sources with vastly increased sensitivity and frequency coverage. This creates the need for major enhancements to laboratory databases for the more prominent interstellar 'weed' species in order to model and account for their lines in observed spectra in the search for new and more exotic interstellar molecular 'flowers'. With its large-amplitude internal torsional motion, methanol has particularly rich spectra throughout the FIR and IR regions and, being very widely distributed throughout the galaxy, is perhaps the most notorious interstellar weed. Thus, we have recorded new spectra for a variety of methanol isotopic species on the high-resolution FTIR spectrometer on the CLS FIR beamline. The aim is to extend quantum number coverage of the data, improve our understanding of the energy level structure, and provide the astronomical community with better databases and models of the spectral patterns with greater predictive power for a range of astrophysical conditions.

  5. Investigation of the coal fly ashes using IR spectroscopy.

    PubMed

    Mozgawa, W; Król, M; Dyczek, J; Deja, J

    2014-11-11

    The results of FT-IR spectroscopic studies of coal fly ashes, originated from various polish power plants are reported. The results of MIR investigations were compared to the X-ray diffraction (XRD) measurements and chemical analyses. They are mainly composed of silica, alumina and lime. The infrared spectrum in the middle range can be used to describe both the structure of phases present in the fly ash and to identify the characteristic elements of the individual components of ash. The results indicate that the amount of aluminosilicate and its Si/Al ratio induce a shift in the T-O stretching band appearing at 950-1100 cm(-1). Moreover, FWHM of these bands indicates the participation of the crystalline phase relative to amorphous. The presence of carbonate phases generates substantial changes in the 1450-1400 cm(-1) area of the spectra. The presence of such phases as anhydrite, mullite or illite has also been established on the basis of IR spectra. PMID:24935825

  6. Continuous measurements of stable carbon isotopes in CO2 with a near-IR laser absorption spectrometer

    NASA Astrophysics Data System (ADS)

    Tanaka, Kotaro; Kojima, Ryota; Takahashi, Kenshi; Tonokura, Kenichi

    2013-09-01

    A near-IR laser absorption spectrometer using a technique of wavelength modulation spectroscopy is used to measure stable carbon isotope ratios of ambient CO2 (δ13C) via the absorption lines 12CO2 R(17) (2ν1 + ν12 - ν12 + ν3) at 4978.205 cm-1 and 13CO2 P(16) (ν1 + 2ν2 + ν3) at 4978.023 cm-1. The isotope ratios are measured with a reproducibility of 0.02‰ (1σ) in a 130-s integration time over a 12-h period. The humidity effect on δ13C values has been evaluated in laboratory experiments. The δ13C values of CO2 in ambient air were measured continuously over 8 days and agreed well with those from isotope ratio mass spectrometry of canister samples. The spectrometer is thus capable of real-time, in situ measurements of stable carbon isotope ratios of CO2 under ambient conditions.

  7. X-ray absorption spectroscopy of liquid surface

    NASA Astrophysics Data System (ADS)

    Watanabe, Iwao; Tanida, Hajime; Kawauchi, Sigehiro; Harada, Makoto; Nomura, Masaharu

    1997-09-01

    An apparatus has been constructed for x-ray absorption spectroscopy of elements at air/aqueous solution interface. Its surface sensitivity is gained from glancing incidence of synchrotron radiation under total reflection condition. The absorption is detected by total conversion He ion-yield method. This apparatus was operated at the beam line 7C of Photon Factory, where the incident photon beam comes from a sagittal focus double-crystal monochromator via a 70-cm-long bent mirror. The mirror focuses the beam vertically and changes the beam direction downward by 1 mrad to irradiate solution surface. The essential requirement of this technique, ripple-free liquid surface at accurate position, was attained by introducing a trough on a floating boat, continuous surface level monitoring, and an automatic Z-stage control. The x-ray absorption edge jump demonstrated that surface concentration of bromide ion follows the Langmuir type adsorption for tetraalkylammonuim bromide solution. By comparing the jump values for surface-active and -inactive bromide salt solutions, the detecting depth of the present technique was determined to be 8.8 nm. An extended x-ray absorption fine structure analysis of bromide ion segregated to the surface by stearyltrimethylammonium cation indicated that its solvation structure is different from that of bulk.

  8. Diagnostic potential of cosmic-neutrino absorption spectroscopy

    SciTech Connect

    Barenboim, Gabriela; Mena Requejo, Olga; Quigg, Chris; /Fermilab

    2004-12-01

    Annihilation of extremely energetic cosmic neutrinos on the relic-neutrino background can give rise to absorption lines at energies corresponding to formation of the electroweak gauge boson Z{sup 0}. The positions of the absorption dips are set by the masses of the relic neutrinos. Suitably intense sources of extremely energetic (10{sup 21} - 10{sup 25}-eV) cosmic neutrinos might therefore enable the determination of the absolute neutrino masses and the flavor composition of the mass eigenstates. Several factors--other than neutrino mass and composition--distort the absorption lines, however. We analyze the influence of the time-evolution of the relic-neutrino density and the consequences of neutrino decay. We consider the sensitivity of the lineshape to the age and character of extremely energetic neutrino sources, and to the thermal history of the Universe, reflected in the expansion rate. We take into account Fermi motion arising from the thermal distribution of the relic-neutrino gas. We also note the implications of Dirac vs. Majorana relics, and briefly consider unconventional neutrino histories. We ask what kinds of external information would enhance the potential of cosmic-neutrino absorption spectroscopy, and estimate the sensitivity required to make the technique a reality.

  9. Operando X-ray absorption and infrared fuel cell spectroscopy

    SciTech Connect

    Lewis, Emily A.; Kendrick, Ian; Jia, Qingying; Grice, Corey; Segre, Carlo U.; Smotkin, Eugene S.

    2011-11-17

    A polymer electrolyte fuel cell enables operando X-ray absorption and infrared spectroscopy of the membrane electrode assembly catalytic layer with flowing fuel and air streams at controlled temperature. Time-dependent X-ray absorption near edge structure spectra of the Pt and Ni edge of Pt based catalysts of an air-breathing cathode show that catalyst restructuring, after a potential step, has time constants from minutes to hours. The infrared Stark tuning plots of CO adsorbed on Pt at 100, 200, 300 and 400 mV vs. hydrogen reference electrode were obtained. The Stark tuning plots of CO adsorbed at 400 mV exhibit a precipitous drop in frequency coincident with the adsorption potential. The turn-down potential decreases relative to the adsorption potential and is approximately constant after 300 mV. These Stark tuning characteristics are attributed to potential dependent adsorption site selection by CO and competitive adsorption processes.

  10. The determination of vanadium in brines by atomic absorption spectroscopy

    USGS Publications Warehouse

    Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

    1971-01-01

    A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

  11. Ir Spectroscopy on Peptides and Proteins after Ion Mobility Selection and in Liquid Helium Droplets

    NASA Astrophysics Data System (ADS)

    von Helden, Gert

    2015-06-01

    IR spectroscopy has become a frequently used tool to characterize gas-phase peptides and proteins. In many experiments, ions are m/z selected, irradiated by intense and tunable IR light and fragmentation is monitored as a function of IR wavelength. The presence of different conformers can, however, complicate the interpretation, as the resulting spectra represent the sum of the spectra of the individual components. We constructed a setup, in which ion mobility methods are used to obtain m/z selected ions of defined shape on which are then further investigated by IR spectroscopy. First results on peptide aggregates are presented and for some of those, the IR spectra show a transition from helical or random coil to beta sheet structures. In a different experiment, peptide or protein ions are captures in liquid helium droplets prior to IR spectroscopic investigation. The conditions inside a helium droplet are isothermal at 0.38 K and the interaction between the helium matrix and the molecules are weak so that only small perturbations on the molecule are expected. IR spectra for m/z selected peptides with up to 10 aminoacids and proteins containing more than 100 aminoacids have been measured. The spectra of the smaller species show resolved bands of individual oscillators, which can be used for structure assignment. For the larger species, band envelopes are obtained and for the case of highly charged proteins, a transition form helical to extended structures is observed.

  12. Spatially resolved concentration measurements based on backscatter absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Ze; Sanders, Scott T.; Robinson, Michael A.

    2016-06-01

    We demonstrate the feasibility of spatially resolved measurements of gas properties using direct absorption spectroscopy in conjunction with backscattered signals. We report a 1-D distribution of H2O mole fraction with a spatial resolution of 5 mm. The peak and average discrepancy between the measured and expected mole fraction are 21.1 and 8.0 %, respectively. The demonstration experiment is related to a diesel aftertreatment system; a selective catalytic reduction brick made of cordierite is used. The brick causes volume scattering interference; advanced baseline fitting based on a genetic algorithm is used to reduce the effects of this interference by a factor of 2.3.

  13. Probing electrons in TiO2 polaronic trap states by IR-absorption: evidence for the existence of hydrogenic states.

    PubMed

    Sezen, Hikmet; Buchholz, Maria; Nefedov, Alexei; Natzeck, Carsten; Heissler, Stefan; Di Valentin, Cristiana; Wöll, Christof

    2014-01-01

    An important step in oxide photochemistry, the loading of electrons into shallow trap states, was studied using infrared (IR) spectroscopy on both, rutile TiO2 powders and single-crystal, r-TiO2(110) oriented samples. After UV-irradiation or n-doping by exposure to H-atoms broad IR absorption lines are observed for the powders at around 940 cm(-1). For the single crystal substrates, the IR absorption bands arising from an excitation of the trapped electrons into higher-lying final states show additional features not observed in previous work. On the basis of our new, high-resolution data and theoretical studies on the polaron binding energy in rutile we propose that the trap states correspond to polarons and are thus intrinsic in nature. We assign the final states probed by the IR-experiments to hydrogenic states within the polaron potential. Implications of these observations for photochemistry on oxides will be briefly discussed. PMID:24448350

  14. Monitoring PVD metal vapors using laser absorption spectroscopy

    SciTech Connect

    Braun, D.G.; Anklam, T.M.; Berzins, L.V.; Hagans, K.G.

    1994-04-01

    Laser absorption spectroscopy (LAS) has been used by the Atomic Vapor Laser Isotope Separation (AVLIS) program for over 10 years to monitor the co-vaporization of uranium and iron in its separators. During that time, LAS has proven to be an accurate and reliable method to monitor both the density and composition of the vapor. It has distinct advantages over other rate monitors, in that it is completely non-obtrusive to the vaporization process and its accuracy is unaffected by the duration of the run. Additionally, the LAS diagnostic has been incorporated into a very successful process control system. LAS requires only a line of sight through the vacuum chamber, as all hardware is external to the vessel. The laser is swept in frequency through an absorption line of interest. In the process a baseline is established, and the line integrated density is determined from the absorption profile. The measurement requires no hardware calibration. Through a proper choice of the atomic transition, a wide range of elements and densities have been monitored (e.g. nickel, iron, cerium and gadolinium). A great deal of information about the vapor plume can be obtained from the measured absorption profiles. By monitoring different species at the same location, the composition of the vapor is measured in real time. By measuring the same density at different locations, the spatial profile of the vapor plume is determined. The shape of the absorption profile is used to obtain the flow speed of the vapor. Finally, all of the above information is used evaluate the total vaporization rate.

  15. Open-path tunable diode laser absorption spectroscopy for acquisition of fugitive emission flux data.

    PubMed

    Thoma, Eben D; Shores, Richard C; Thompson, Edgar L; Harris, D Bruce; Thorneloe, Susan A; Varma, Ravi M; Hashmonay, Ram A; Modrak, Mark T; Natschke, David F; Gamble, Heather A

    2005-05-01

    Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented. PMID:15991674

  16. Surface characterization of Kevlar fibers by FT-IR spectroscopy

    SciTech Connect

    Chatzi, E.G.

    1987-01-01

    The Kevlar-49 aramid fiber offers considerable potential for utilization in high-performance composite materials. However, it has poor adhesion to the polymer matrix resin. In order to improve the adhesion the surface of the fiber was characterized by using two nondestructive Fourier transform infrared (FT-IR) techniques. It was shown that the polymer chains in the skin are oriented parallel to the surface, while in the core they are almost radially oriented. This orientation as well as the fact that the functional groups are intermolecularly hydrogen-bonded might limit their availability for reacting with the polymer matrix. The author also characterized the water absorbed in both the skin and the core of the fiber and found the existence of three types of water: (a) weakly hydrogen-bonded between one NH and one carbonyl group, (b) between two carbonyl groups and (c) liquid-like water clustered in microvoids and other sites inside the fibers. It was also found that 30% of the NH groups of the Kevlar-49 fiber are accessible for deuterium exchange. These groups on one hand are available for reactions that would improve the adhesion, but on the other hand can hydrogen-bond with water, which would be detrimental for the mechanical properties of the composite.

  17. Mid-infrared absorption spectroscopy using quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Haibach, Fred; Erlich, Adam; Deutsch, Erik

    2011-06-01

    Block Engineering has developed an absorption spectroscopy system based on widely tunable Quantum Cascade Lasers (QCL). The QCL spectrometer rapidly cycles through a user-selected range in the mid-infrared spectrum, between 6 to 12 μm (1667 to 833 cm-1), to detect and identify substances on surfaces based on their absorption characteristics from a standoff distance of up to 2 feet with an eye-safe laser. It can also analyze vapors and liquids in a single device. For military applications, the QCL spectrometer has demonstrated trace explosive, chemical warfare agent (CWA), and toxic industrial chemical (TIC) detection and analysis. The QCL's higher power density enables measurements from diffuse and highly absorbing materials and substrates. Other advantages over Fourier Transform Infrared (FTIR) spectroscopy include portability, ruggedness, rapid analysis, and the ability to function from a distance through free space or a fiber optic probe. This paper will discuss the basic technology behind the system and the empirical data on various safety and security applications.

  18. IR spectroscopy of water vapor confined in nanoporous silica aerogel.

    PubMed

    Ponomarev, Yu N; Petrova, T M; Solodov, A M; Solodov, A A

    2010-12-01

    The absorption spectrum of the water vapor, confined in the nanoporous silica aerogel, was measured within 5000-5600 cm(-1) with the IFS 125 HR Fourier spectrometer. It has been shown, that tight confinement of the molecules by the nanoporous size leads to the strong lines broadening and shift. For water vapor lines, the HWHM of confined molecules are on the average 23 times larger than those for free molecules. The shift values are in the range from -0.03 cm(-1) to 0.09 cm(-1). Some spectral lines have negative shift. The data on the half-widths and center shifts for some strongest H(2)O lines have been presented. PMID:21164954

  19. Detection of cancerous biological tissue areas by means of infrared absorption and SERS spectroscopy of intercellular fluid

    NASA Astrophysics Data System (ADS)

    Velicka, M.; Urboniene, V.; Ceponkus, J.; Pucetaite, M.; Jankevicius, F.; Sablinskas, V.

    2015-08-01

    We present a novel approach to the detection of cancerous kidney tissue areas by measuring vibrational spectra (IR absorption or SERS) of intercellular fluid taken from the tissue. The method is based on spectral analysis of cancerous and normal tissue areas in order to find specific spectral markers. The samples were prepared by sliding the kidney tissue over a substrate - surface of diamond ATR crystal in case of IR absorption or calcium fluoride optical window in case of SERS. For producing the SERS signal the dried fluid film was covered by silver nanoparticle colloidal solution. In order to suppress fluorescence background the measurements were performed in the NIR spectral region with the excitation wavelength of 1064 nm. The most significant spectral differences - spectral markers - were found in the region between 400 and 1800 cm-1, where spectral bands related to various vibrations of fatty acids, glycolipids and carbohydrates are located. Spectral markers in the IR and SERS spectra are different and the methods can complement each other. Both of them have potential to be used directly during surgery. Additionally, IR absorption spectroscopy in ATR mode can be combined with waveguide probe what makes this method usable in vivo.

  20. High Resolution Near-IR Spectroscopy of Protostars With Large Telescopes

    NASA Technical Reports Server (NTRS)

    Greene, Tom; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    It is now possible to measure absorption spectra of Class I protostars using D greater than or = 8m telescopes equipped with sensitive cryogenic IR spectrographs. Our latest high-resolution (R approx. 20,000) Keck data reveal that Class I protostars are indeed low-mass stars with dwarf-like features. However, they differ from T Tauri stars in that Class I protostars have much higher IR veilings (tau(sub k) greater than or = 1 - 3+) and they are rotating quickly, v sin i greater than 20 km/s. Interestingly, the vast majority of protostellar absorption spectra show stellar - not disk - absorption features. A preliminary H-R diagram suggests that protostellar photospheres may have different physical structures than T Tauri stars, perhaps due to their higher accretion rates.

  1. [Retrieval of monocyclic aromatic hydrocarbons with differential optical absorption spectroscopy].

    PubMed

    Xie, Pin-Hua; Fu, Qiang; Liu, Jian-Guo; Liu, Wen-Qing; Qin, Min; Li, Ang; Liu, Shi-Sheng; Wei, Qing-Nong

    2006-09-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range, e. g. SO2, NO2, O3 etc. However, unlike the absorption spectra of SO2 and NO2, the analysis of aromatic compounds is difficult and strongly suffers from the cross interference of other absorbers (Herzberg bands of oxygen, ozone and sulfur dioxide), especially with relatively low concentrations of aromatic compounds in the atmosphere. In the present paper, the DOAS evaluation of aromatic compounds was performed by nonlinear least square fit with two interpolated oxygen optical density spectra at different path lengths and reference spectra of ozone at different temperature and SO2 cross section to correct the interference from absorbers of O2, O3 and SO2. The measurement of toluene, benzene, (m, p, o) xylene and phenol with a DOAS system showed that DOAS method is suitable for monocyclic aromatic compounds monitoring in the atmosphere. PMID:17112022

  2. Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

    NASA Astrophysics Data System (ADS)

    Kuntermann, Volker; Cimpean, Carla; Brehm, Georg; Sauer, Guido; Kryschi, Carola; Wiggers, Hartmut

    2008-03-01

    Excitonic properties of colloidal silicon quantum dots (Si qdots) with mean sizes of 4nm were examined using stationary and time-resolved optical spectroscopy. Chemically stable silicon oxide shells were prepared by controlled surface oxidation and silanization of HF-etched Si qdots. The ultrafast relaxation dynamics of photogenerated excitons in Si qdot colloids were studied on the picosecond time scale from 0.3psto2.3ns using femtosecond-resolved transient absorption spectroscopy. The time evolution of the transient absorption spectra of the Si qdots excited with a 150fs pump pulse at 390nm was observed to consist of decays of various absorption transitions of photoexcited electrons in the conduction band which overlap with both the photoluminescence and the photobleaching of the valence band population density. Gaussian deconvolution of the spectroscopic data allowed for disentangling various carrier relaxation processes involving electron-phonon and phonon-phonon scatterings or arising from surface-state trapping. The initial energy and momentum relaxation of hot carriers was observed to take place via scattering by optical phonons within 0.6ps . Exciton capturing by surface states forming shallow traps in the amorphous SiOx shell was found to occur with a time constant of 4ps , whereas deeper traps presumably localized in the Si-SiOx interface gave rise to exciton trapping processes with time constants of 110 and 180ps . Electron transfer from initially populated, higher-lying surface states to the conduction band of Si qdots (>2nm) was observed to take place within 400 or 700fs .

  3. Optimized interferometric setup for chiral and achiral ultrafast IR spectroscopy.

    PubMed

    Dutta, Biplab; Helbing, Jan

    2015-06-15

    We report an actively stabilized interferometer-based set-up for the detection of vibrational circular dichroism (VCD) and optical rotatory dispersion (VORD) with femtosecond laser pulses. Our approach combines and improves elements of several previous measurement strategies, including signal amplification in a crossed polarizer configuration, precise control and modulation of polarization, phase stability, tight focusing, broad-band detection and spectral interferometry. Their importance for static and transient measurements is motivated by a signal analysis based on Jones matrices and response theory. Only depending on the pump-beam polarization, the set-up can selectively detect transient VCD and VORD or transient linear birefringence (LB) and linear dichroism (LD), which usually constitute the dominant artifacts in the chiral measurements. For illustration we present transient LB and LD data of an achiral Rhenium carbonyl complex, detected simultaneously by spectral interferometry, and we analyze residual background signals in the experimental configuration for transient chiral spectroscopy. PMID:26193616

  4. Optical re-injection in cavity-enhanced absorption spectroscopy

    PubMed Central

    Leen, J. Brian; O’Keefe, Anthony

    2014-01-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10−10 cm−1/\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}$\\sqrt {{\\rm Hz;}}$\\end{document} Hz ; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features. PMID:25273701

  5. Optical re-injection in cavity-enhanced absorption spectroscopy.

    PubMed

    Leen, J Brian; O'Keefe, Anthony

    2014-09-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10(-10) cm(-1)/√Hz; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features. PMID:25273701

  6. Optical re-injection in cavity-enhanced absorption spectroscopy

    SciTech Connect

    Leen, J. Brian O’Keefe, Anthony

    2014-09-15

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10{sup −10} cm{sup −1}/√(Hz;) an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features.

  7. WATER ABSORPTION FROM GAS VERY NEAR THE MASSIVE PROTOSTAR AFGL 2136 IRS 1

    SciTech Connect

    Indriolo, Nick; Neufeld, D. A.; Seifahrt, A.; Richter, M. J.

    2013-10-10

    We present ground-based observations of the ν{sub 1} and ν{sub 3} fundamental bands of H{sub 2}O toward the massive protostar AFGL 2136 IRS 1, identifying absorption features due to 47 different ro-vibrational transitions between 2.468 μm and 2.561 μm. Analysis of these features indicates the absorption arises in warm (T = 506 ± 25 K), very dense (n(H{sub 2}) > 5 × 10{sup 9} cm{sup –3}) gas, suggesting an origin close to the central protostar. The total column density of warm water is estimated to be N(H{sub 2}O) = (1.02 ± 0.02) × 10{sup 19} cm{sup –2}, giving a relative abundance of N(H{sub 2}O)/N(H{sub 2}) ≈ 10{sup –4}. Our study represents the first extensive use of water vapor absorption lines in the near infrared, and demonstrates the utility of such observations in deriving physical parameters.

  8. Detection of starch adulteration in onion powder by FT-NIR and FT-IR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Adulteration of onion powder with cornstarch was identified by Fourier transform near-infrared (FT-NIR) and Fourier transform infrared (FT-IR) spectroscopy. The reflectance spectra of 180 pure and adulterated samples (1–35 wt% starch) were collected and preprocessed to generate calibration and predi...

  9. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  10. Allophane on Mars: Evidence from IR Spectroscopy and TES Spectral Models

    NASA Technical Reports Server (NTRS)

    Ming, Douglas W.; Rampe, E. B.; Kraft, M. D.; Sharp. T. G.; Golden, D. C.; Christensen, P. C.

    2010-01-01

    Allophane is an alteration product of volcanic glass and a clay mineral precursor that is commonly found in basaltic soils on Earth. It is a poorly-crystalline or amorphous, hydrous aluminosilicate with Si/Al ratios ranging from approx.0.5-1 [Wada, 1989]. Analyses of thermal infrared (TIR) spectra of the Martian surface from TES show high-silica phases at mid-to-high latitudes that have been proposed to be primary volcanic glass [Bandfield et al., 2000; Bandfield, 2002; Rogers and Christensen, 2007] or poorly-crystalline secondary silicates such as allophane or aluminous amorphous silica [Kraft et al., 2003; Michalski et al., 2006; Rogers and Christensen, 2007; Kraft, 2009]. Phase modeling of chemical data from the APXS on the Mars Exploration Rover Spirit suggest the presence of allophane in chemically weathered rocks [Ming et al., 2006]. The presence of allophane on Mars has not been previously tested with IR spectroscopy because allophane spectra have not been available. We synthesized allophanes and allophanic gels with a range of Si/Al ratios to measure TIR emission and VNIR reflectance spectra and to test for the presence of allophane in Martian soils. VNIR reflectance spectra of the synthetic allophane samples have broad absorptions near 1.4 m from OH stretching overtones and 1.9 m from a combination of stretching and bending vibrations in H2O. Samples have a broad absorption centered near 2.25 microns, from AlAlOH combination bending and stretching vibrations, that shifts position with Si/Al ratio. Amorphous silica (opaline silica or primary volcanic glass) has been identified in CRISM spectra of southern highland terrains based on the presence of 1.4, 1.9, and broad 2.25 m absorptions [Mustard et al., 2008]; however, these absorptions are also consistent with the presence of allophane. TIR emission spectra of the synthetic allophanes show two spectrally distinct types: Si-rich and Al-rich. Si-rich allophanes have two broad absorptions centered near 1080

  11. Improved Sensitivity for Frequency Modulation Laser Absorption Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Shum, Chi-Man

    1990-01-01

    We have developed and implemented a two-tone harmonic frequency modulation technique to reduce the residue amplitude modulation (RAM) background in frequency modulation (FM) laser absorption spectroscopy. This RAM noise, generated during electro-optically phase modulating the laser carrier, is several orders of magnitude larger than the shot-noise detection limit. When our two-tone method was used, the RAM signal was reduced by a factor of 4. We have also provided a thorough signal-to-noise analysis which leads to a detection limit consistent with out experimental results. A vital element in the work of FM spectroscopy is the electro-optic phase modulator. We have designed and fabricated two phase modulators, both employing a lithium tantalate single crystal. The first device is a broad -band design called the traveling wave phase modulator. With microstrip transmission line construction techniques, the impedance of the device is matched to 50 Omega within a bandwidth of more than 500 MHz. The second modulator was a novel design built to provide enhanced modulation index at a resonant frequency tunable over a frequency range of approximately 350 MHz. This resonant modulator can provide the same modulation efficiency as that from the traveling wave device with as much as 50% less modulation power. Both modulators have useful applications in FM spectroscopy depending on the experimental conditions.

  12. Ground-Based IR Spectroscopy of Mercury for Composition

    NASA Technical Reports Server (NTRS)

    Killen, Rosemary M.

    2001-01-01

    Remote sensing measurements of the Moon and Mercury in the thermal infrared have been plagued with problems due to atmospheric absorption and other effects. Controversial results have been discussed by Nash et al. and by Salisbury et al.. We have developed a technique to obtain thermal infrared spectra of Mercury together with solar and sky spectra in the 8-13 micrometer region suitable for determining the presence or absence of mineralogical features. High-resolution (0.05 cm(exp -1) between data points) spectra were obtained during daylight using the Fourier Transform Spectrograph (FTS) at the McMath-Pierce Solar Telescope Facility at Kitt Peak National Observatory, Arizona. The reduced data were independent of any model of the transmission of the Earth's atmosphere and rest on a calibration using sky spectra along the same line-of-sight through the atmosphere as the actual Mercury raw spectrum. This method can be applied at all solar elongation angles including small elongation angles (5 deg or less). The basic sequence and the technique are robust.

  13. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface.

    PubMed

    Erikat, I A; Hamad, B A

    2013-11-01

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir-C and Ir-Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule. PMID:24206318

  14. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

    NASA Astrophysics Data System (ADS)

    Erikat, I. A.; Hamad, B. A.

    2013-11-01

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir-C and Ir-Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

  15. Monitoring of volcanic sulphur dioxide emissions using differential absorption lidar (DIAL), differential optical absorption spectroscopy (DOAS), and correlation spectroscopy (COSPEC)

    NASA Astrophysics Data System (ADS)

    Weibring, P.; Edner, H.; Svanberg, S.; Cecchi, G.; Pantani, L.; Ferrara, R.; Caltabiano, T.

    1998-10-01

    The total fluxes of sulphur dioxide from the Italian volcanoes Etna, Stromboli, and Vulcano were studied using optical remote sensing techniques in three shipborne field experiments (1992, 1994, and 1997). The main purpose of the experiments was to compare active (laser) techniques with passive monitoring. Differential absorption lidar (DIAL) measurements were implemented by placing the Swedish mobile lidar system on board the Italian research vessel Urania, sailing under the volcanic plumes. Simultaneously, the passive differential optical absorption spectroscopy (DOAS) technique was used for assessing the total overhead gas burden. Finally, correlation spectroscopy (COSPEC) was also implemented in one of the campaigns. Differences in integrated gas column assessment are expected and observed, mostly connected to complex scattering conditions influencing the passive measurements. Since such measurements are much employed in routine volcanic monitoring it is of great interest to model and provide corrections to the raw data obtained. Lidar measurements proved to be quite useful for this purpose. By combining the integrated gas concentration over the plume cross section with wind velocity data, SO2 fluxes of the order of 1000, 100, and 10 tonnes/day were measured for Mt. Etna, Stromboli, and Vulcano, respectively.

  16. Photoisomerization and structural dynamics of two nitrosylruthenium complexes: a joint study by NMR and nonlinear IR spectroscopies.

    PubMed

    Wang, Jianru; Yang, Fan; Zhao, Yan; Yu, Pengyun; Qiao, Xiaoyan; Wang, Jianping; Wang, Hongfei

    2014-11-21

    In this work, the photoisomerization and structural dynamics of two isomeric nitrosylruthenium(ii) complexes [Ru(OAc)(2cqn)2NO] (H2cqn = 2-chloro-8-quinolinol) in CDCl3 and DMSO are examined using NMR and IR spectroscopic methods. The two N atoms in the 2cqn ligand are in trans position in the synthesized cis-1 isomer, while they are in cis position in the cis-2 isomer. Kinetics monitored by NMR spectroscopy shows that the rate constant of photoisomerization from cis-2 to cis-1 isomer depends on the wavelength of irradiation and solvent polarity; it proceeds faster on irradiating near the absorption peak in the UV-Vis region, and also in more polar solvents (DMSO). Density functional theory computation indicates that the peculiarity of [Ru(ii)-NO(+)] group affects the structure and reactivity of the nitrosylruthenium complexes. Using the nitrosyl stretching (νNO) to be vibrational probe, the structural dynamics and structural distributions of the cis-1 and cis-2 isomers are examined by steady-state linear infrared and ultrafast two-dimensional infrared (2D IR) spectroscopies. The structural and photochemical aspects of the observed spectroscopic parameters are discussed in terms of solute-solvent interactions for the two nitrosylruthenium complexes. PMID:25285659

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Sub millimeter absorption spectroscopy of oxygen containing fluorocarbon etching plasmas

    NASA Astrophysics Data System (ADS)

    Benck, Eric; Siegrist, Karen

    2004-09-01

    The role of oxygen in fluorocarbon etching plasmas is investigated using sub millimeter wavelength absorption spectroscopy. The plasmas were created in a specially modified capacitively coupled Gaseous Electronics Conference (GEC) Reference Reactor with a commercial electrostatic chuck. Photoresist and SiO2 blanket coated wafers were etched in C_4F_8/O_2/Ar, C_5F_8/O_2/Ar, and C_4F_6/O_2/Ar discharges. The absolute density of various radicals (CF, CF_2, CHF_3, COF_2, CO, etc.) were measured as a function of the percentage of oxygen in the feed gas mixture using a sub millimeter source based on a 48x frequency multiplication chain. These results are also compared with C_xF_y/O_2/Xe mixtures.

  19. La Saturated Absorption Spectroscopy for Applications in Quantum Information

    NASA Astrophysics Data System (ADS)

    Becker, Patrick; Donoghue, Liz; Dungan, Kristina; Liu, Jackie; Olmschenk, Steven

    2015-05-01

    Quantum information may revolutionize computation and communication by utilizing quantum systems based on matter quantum bits and entangled light. Ions are excellent candidates for quantum bits as they can be well-isolated from unwanted external influences by trapping and laser cooling. Doubly-ionized lanthanum in particular shows promise for use in quantum information as it has infrared transitions in the telecom band, with low attenuation in standard optical fiber, potentially allowing for long distance information transfer. However, the hyperfine splittings of the lowest energy levels, required for laser cooling, have not been measured. We present progress and recent results towards measuring the hyperfine splittings of these levels in lanthanum by saturated absorption spectroscopy with a hollow cathode lamp. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

  20. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

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

    2006-10-27

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

  1. High Resolution Absorption Spectroscopy using Externally Dispersed Interferometry

    SciTech Connect

    Edelstein, J; Erskine, D J

    2005-07-06

    We describe the use of Externally Dispersed Interferometry (EDI) for high-resolution absorption spectroscopy. By adding a small fixed-delay interferometer to a dispersive spectrograph, a precise fiducial grid in wavelength is created over the entire spectrograph bandwidth. The fiducial grid interacts with narrow spectral features in the input spectrum to create a moire pattern. EDI uses the moire pattern to obtain new information about the spectra that is otherwise unavailable, thereby improving spectrograph performance. We describe the theory and practice of EDI instruments and demonstrate improvements in the spectral resolution of conventional spectrographs by a factor of 2 to 6. The improvement of spectral resolution offered by EDI can benefit space instruments by reducing spectrograph size or increasing instantaneous bandwidth.

  2. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy.

    PubMed

    Serrano, A; Rodríguez de la Fuente, O; Collado, V; Rubio-Zuazo, J; Monton, C; Castro, G R; García, M A

    2012-08-01

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10(-3) to 10(-5), depending on the particular experiment. PMID:22938268

  3. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  4. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals

    SciTech Connect

    Curl, Robert F; Glass, Graham

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  5. Remote Thermal IR Spectroscopy of our Solar System

    NASA Technical Reports Server (NTRS)

    Kostiuk, Theodor; Hewagama, Tilak; Goldstein, Jeffrey; Livengood, Timothy; Fast, Kelly

    1999-01-01

    Indirect methods to detect extrasolar planets have been successful in identifying a number of stars with companion planets. No direct detection of an extrasolar planet has yet been reported. Spectroscopy in the thermal infrared region provides a potentially powerful approach to detection and characterization of planets and planetary systems. We can use knowledge of our own solar system, its planets and their atmospheres to model spectral characteristics of planets around other stars. Spectra derived from modeling our own solar system seen from an extrasolar perspective can be used to constrain detection strategies, identification of planetary class (terrestrial vs. gaseous) and retrieval of chemical, thermal and dynamical information. Emission from planets in our solar system peaks in the thermal infrared region, approximately 10 - 30 microns, substantially displaced from the maximum of the much brighter solar emission in the visible near 0.5 microns. This fact provides a relatively good contrast ratio to discriminate between stellar (solar) and planetary emission and optimize the delectability of planetary spectra. Important molecular constituents in planetary atmospheres have rotational-vibrational spectra in the thermal infrared region. Spectra from these molecules have been well characterized in the laboratory and studied in the atmospheres of solar system planets from ground-based and space platforms. The best example of such measurements are the studies with Fourier transform spectrometers, the Infrared Interferometer Spectrometers (IRIS), from spacecraft: Earth observed from NIMBUS 8, Mars observed from Mariner 9, and the outer planets observed from Voyager spacecraft. An Earth-like planet is characterized by atmospheric spectra of ozone, carbon dioxide, and water. Terrestrial planets have oxidizing atmospheres which are easily distinguished from reducing atmospheres of gaseous giant planets which lack oxygen-bearing species and are characterized by spectra

  6. Temperature and pressure measurement based on tunable diode laser absorption spectroscopy with gas absorption linewidth detection

    NASA Astrophysics Data System (ADS)

    Meng, Yunxia; Liu, Tiegen; Liu, Kun; Jiang, Junfeng; Wang, Tao; Wang, Ranran

    2014-11-01

    A gas temperature and pressure measurement method based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) detecting linewidth of gas absorption line was proposed in this paper. Combined with Lambert-Beer Law and ideal gas law, the relationship between temperature, pressure and gas linewidth with Lorentzian line shape was investigated in theory. Taking carbon monoxide (CO) at 1567.32 nm for example, the linewidths of gas absorption line in different temperatures and pressures were obtained by simulation. The relationship between the linewidth of second harmonic and temperature, pressure with the coefficient 0.025 pm/K and 0.0645 pm/kPa respectively. According to the relationship of simulation results and detected linewidth, the undefined temperature and pressure of CO gas were measured. The gas temperature and pressure measurement based on linewidth detection, avoiding the influence of laser intensity, is an effective temperature and pressure measurement method. This method also has the ability to detect temperature and pressure of other gases with Lorentzian line shape.

  7. High-dispersion absorption-line spectroscopy of AE Aqr

    NASA Astrophysics Data System (ADS)

    Echevarría, J.; Smith, Robert Connon; Costero, R.; Zharikov, S.; Michel, R.

    2008-07-01

    High-dispersion time-resolved spectroscopy of the unique magnetic cataclysmic variable AE Aqr is presented. A radial velocity analysis of the absorption lines yields K2 = 168.7 +/- 1kms-1. Substantial deviations of the radial velocity curve from a sinusoid are interpreted in terms of intensity variations over the secondary star's surface. A complex rotational velocity curve as a function of orbital phase is detected which has a modulation frequency of twice the orbital frequency, leading to an estimate of the binary inclination angle that is close to 70°. The minimum and maximum rotational velocities are used to indirectly derive a mass ratio of q = 0.6 and a radial velocity semi-amplitude of the white dwarf of K1 = 101 +/- 3kms-1. We present an atmospheric temperature indicator, based on the absorption-line ratio of FeI and CrI lines, whose variation indicates that the secondary star varies from K0 to K4 as a function of orbital phase. The ephemeris of the system has been revised, using more than 1000 radial velocity measurements, published over nearly five decades. From the derived radial velocity semi-amplitudes and the estimated inclination angle, we calculate that the masses of the stars are M1 = 0.63 +/- 0.05Msolar M2 = 0.37 +/- 0.04Msolar, and their separation is a = 2.33 +/- 0.02Rsolar. Our analysis indicates the presence of a late-type star whose radius is larger, by a factor of nearly 2, than the radius of a normal main-sequence star of the same mass. Finally, we discuss the possibility that the measured variations in the rotational velocity, temperature and spectral type of the secondary star as functions of orbital phase may, like the radial velocity variations, be attributable to regions of enhanced absorption on the star's surface.

  8. Characterization of inorganic species in coal by laser-induced breakdown spectroscopy using UV and IR radiations

    NASA Astrophysics Data System (ADS)

    Mateo, M. P.; Nicolas, G.; Yañez, A.

    2007-12-01

    In this work, the capability of laser-induced breakdown spectroscopy for process control in a thermal power plant is presented through quantitative compositional characterization of the coal used for combustion. Laser-induced emission signal of seven samples with a range of concentrations was calibrated for quantification purposes. The eighth sample was subsequently analyzed five times as unknown in order to determine the precision and accuracy of the measurements. Two modes of operation, dynamic and static and two laser wavelengths, 1064 nm and 355 nm were employed in this study for comparison. The results revealed that UV wavelength provided better results than IR radiation in terms of accuracy for the quantification of inorganic species in coal after the comparison with conventional atomic absorption spectrometry characterization.

  9. IR multiphoton absorption of SF6 in flow with Ar at moderate energy fluences

    NASA Astrophysics Data System (ADS)

    Makarov, G. N.; Ronander, E.; van Heerden, S. P.; Gouws, M.; van der Merwe, K.

    1997-10-01

    IR multiple photon absorption (MPA) of SF6 in flow with Ar (SF6: Ar=1:100) in conditions of a large vibrational/rotational temperature difference (TV𪒮 K, TR䏐 K) was studied at moderate energy fluences from ۂ.1 to 𪐬 mJ/cm2, which are of interest for isotope selective two-step dissociation of molecules. A 50 cm Laval-type slit nozzle for the flow cooling, and a TEA CO2-laser for excitation of molecules were used in the experiments. The laser energy fluence dependences of the SF6 MPA were studied for several CO2-laser lines which are in a good resonance with the linear absorption spectrum of the Ƚ vibration of SF6 at low temperature. The effect of the laser pulse duration (intensity) on MPA of flow cooled SF6 with Ar was also studied. The results are compared with those obtained in earlier studies.

  10. Rapid identification of Pterocarpus santalinus and Dalbergia louvelii by FTIR and 2D correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Fang-Da; Xu, Chang-Hua; Li, Ming-Yu; Huang, An-Min; Sun, Su-Qin

    2014-07-01

    Since Pterocarpus santalinus and Dalbergia louvelii, which are of precious Rosewood, are very similar in their appearance and anatomy characteristics, cheaper Hongmu D. louvelii is often illegally used to impersonate valuable P. santalinus, especially in Chinese furniture manufacture. In order to develop a rapid and effective method for easy confused wood furniture differentiation, we applied tri-step identification method, i.e., conventional infrared spectroscopy (FT-IR), second derivative infrared (SD-IR) spectroscopy and two-dimensional correlation infrared (2DCOS-IR) spectroscopy to investigate P. santalinus and D. louvelii furniture. According to FT-IR and SD-IR spectra, it has been found two unconditional stable difference at 848 cm-1 and 700 cm-1 and relative stable differences at 1735 cm-1, 1623 cm-1, 1614 cm-1, 1602 cm-1, 1509 cm-1, 1456 cm-1, 1200 cm-1, 1158 cm-1, 1055 cm-1, 1034 cm-1 and 895 cm-1 between D. louvelii and P. santalinus IR spectra. The stable discrepancy indicates that the category of extractives is different between the two species. Besides, the relative stable differences imply that the content of holocellulose in P. santalinus is more than that of D. louvelii, whereas the quantity of extractives in D. louvelii is higher. Furthermore, evident differences have been observed in their 2DCOS-IR spectra of 1550-1415 cm-1 and 1325-1030 cm-1. P. santalinus has two strong auto-peaks at 1459 cm-1 and 1467 cm-1, three mid-strong auto-peaks at 1518 cm-1, 1089 cm-1 and 1100 cm-1 and five weak auto-peaks at 1432 cm-1, 1437 cm-1, 1046 cm-1, 1056 cm-1 and 1307 cm-1 while D. louvelii has four strong auto-peaks at 1465 cm-1, 1523 cm-1, 1084 cm-1 and 1100 cm-1, four mid-strong auto-peaks at 1430 cm-1, 1499 cm-1, 1505 cm-1 and 1056 cm-1 and two auto-peaks at 1540 cm-1 and 1284 cm-1. This study has proved that FT-IR integrated with 2DCOS-IR could be applicable for precious wood furniture authentication in a direct, rapid and holistic manner.

  11. Detection of metanil yellow contamination in turmeric using FT-Raman and FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Dhakal, Sagar; Chao, Kuanglin; Qin, Jianwei; Kim, Moon; Schmidt, Walter; Chan, Dian

    2016-05-01

    Turmeric is well known for its medicinal value and is often used in Asian cuisine. Economically motivated contamination of turmeric by chemicals such as metanil yellow has been repeatedly reported. Although traditional technologies can detect such contaminants in food, high operational costs and operational complexities have limited their use to the laboratory. This study used Fourier Transform Raman Spectroscopy (FT-Raman) and Fourier Transform - Infrared Spectroscopy (FT-IR) to identify metanil yellow contamination in turmeric powder. Mixtures of metanil yellow in turmeric were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1% and 0.01% (w/w). The FT-Raman and FT-IR spectral signal of pure turmeric powder, pure metanil yellow powder and the 8 sample mixtures were obtained and analyzed independently to identify metanil yellow contamination in turmeric. The results show that FT-Raman spectroscopy and FT-IR spectroscopy can detect metanil yellow mixed with turmeric at concentrations as low as 1% and 5%, respectively, and may be useful for non-destructive detection of adulterated turmeric powder.

  12. Determination of the aromatic compounds in plant cuticular waxes using FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Dubis, Eligiusz N.; Dubis, Alina T.; Popławski, J.

    2001-09-01

    The infrared study of the aromatic components of hops ( Humulus lupulus) cuticular wax was performed. HATR FT-IR technique for fresh leaves and their extract analysis was applied. Phenylmethyl myristate, 2-phenylethyl myristate and docosyl benzoate were synthesized and used as reference standards. An absorption band in the range of 709-966 cm -1 indicates the presence of aromatic esters in plant cuticular waxes.

  13. Structural modifications of Tilia cordata wood during heat treatment investigated by FT-IR and 2D IR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Popescu, Maria-Cristina; Froidevaux, Julien; Navi, Parviz; Popescu, Carmen-Mihaela

    2013-02-01

    It is known that heat treatment of wood combined with a low percent of relative humidity causes transformations in the chemical composition of it. The modifications and/or degradation of wood components occur by hydrolysis, oxidation, and decarboxylation reactions. The aim of this study was to give better insights on wood chemical modifications during wood heat treatment under low temperature at about 140 °C and 10% percentage of relative humidity, by infrared, principal component analysis and two dimensional infrared correlation spectroscopy. For this purpose, hardwood samples of lime (Tilia cordata) were investigated and analysed. The infrared spectra of treated samples were compared with the reference ones, the most important differences being observed in the "fingerprint" region. Due to the complexity of this region, which have contributions from all the wood constituents the chemical changes during hydro-thermal treatment were examined in detail using principal component analysis and 2D IR correlation spectroscopy. By hydro-thermal treatment of wood results the formation of acetic acid, which catalyse the hydrolysis reactions of hemicelluloses and amorphous cellulose. The cleavage of the β-O-4 linkages and splitting of the aliphatic methoxyl chains from the aromatic lignin ring was also observed. For the first treatment interval, a higher extent of carbohydrates degradation was observed, then an increase of the extent of the lignin degradation also took place.

  14. Attosecond XUV absorption spectroscopy of doubly excited states in helium atoms dressed by a time-delayed femtosecond infrared laser

    NASA Astrophysics Data System (ADS)

    Yang, Z. Q.; Ye, D. F.; Ding, Thomas; Pfeifer, Thomas; Fu, L. B.

    2015-01-01

    In the present paper, we investigate the time-resolved transient absorption spectroscopy of doubly excited states of helium atoms by solving the time-dependent two-electron Schrödinger equation numerically based on a one-dimensional model. The helium atoms are subjected to an extreme ultraviolet (XUV) attosecond pulse and a time-delayed infrared (IR) few-cycle laser pulse. A superposition of doubly excited states populated by the XUV pulse is identified, which interferes with the direct ionization pathway leading to Fano resonance profiles in the photoabsorption spectrum. In the presence of an IR laser, however, the Fano line profiles are strongly modified: A shifting, splitting, and broadening of the original absorption lines is observed when the XUV attosecond pulse and infrared few-cycle laser pulse overlap in time, which is in good agreement with recent experimental results. At certain time delays, we observe symmetric Lorentz, inverted Fano profiles, and even negative absorption cross sections indicating that the XUV light can be amplified during the interaction with atoms. We further prove that the above pictures are general for different doubly excited states by suitably varying the frequency of the IR field to coherently couple the corresponding states.

  15. Gas in Scattering Media Absorption Spectroscopy -- Laser Spectroscopy in Unconventional Environments

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2010-02-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. The GASMAS technique combines narrow-band diode-laser spectroscopy with optical propagation in diffuse media. Whereas solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures. These are typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. Molecular oxygen and water vapor have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied, demonstrating new possibilities for characterization and diagnostics. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen gas, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the human sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen, while breathing normally through the mouth. A clinical study comprising 40 patients has been concluded.

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

    NASA Astrophysics Data System (ADS)

    Zhao, W.; Chu, W. S.; Yang, F. F.; Yu, M. J.; Chen, D. L.; Guo, X. Y.; Zhou, D. W.; Shi, N.; Marcelli, A.; Niu, L. W.; Teng, M. K.; Gong, W. M.; Benfatto, M.; Wu, Z. Y.

    2007-09-01

    The last several years have witnessed a tremendous increase in biological applications using X-ray absorption spectroscopy (BioXAS), thanks to continuous advancements in synchrotron radiation (SR) sources and detector technology. However, XAS applications in many biological systems have been limited by the intrinsic limitations of the Extended X-ray Absorption Fine Structure (EXAFS) technique e.g., the lack of sensitivity to bond angles. As a consequence, the application of the X-ray absorption near-edge structure (XANES) spectroscopy changed this scenario that is now continuously changing with the introduction of the first quantitative XANES packages such as Minut XANES (MXAN). Here we present and discuss the XANES code MXAN, a novel XANES-fitting package that allows a quantitative analysis of experimental data applied to Zn K-edge spectra of two metalloproteins: Leptospira interrogans Peptide deformylase ( LiPDF) and acutolysin-C, a representative of snake venom metalloproteinases (SVMPs) from Agkistrodon acutus venom. The analysis on these two metallohydrolases reveals that proteolytic activities are correlated to subtle conformation changes around the zinc ion. In particular, this quantitative study clarifies the occurrence of the LiPDF catalytic mechanism via a two-water-molecules model, whereas in the acutolysin-C we have observed a different proteolytic activity correlated to structural changes around the zinc ion induced by pH variations.

  17. Analysis of biological and chemical compounds by remote spectroscopy using IR TeX glass fibers

    NASA Astrophysics Data System (ADS)

    Le Foulgoc, Karine; Le Neindre, Lydia; Guimond, Yann; Ma, Hong Li; Zhang, Xhang H.; Lucas, Jacques

    1995-09-01

    The TeX glasses are attracting much attention as materials for low loss mid-IR optical fibers and are consequently good candidates for thermal imaging, laser power delivery, and more recently remote sensing. The TeX glass fiber, transmitting in a wide optical window, has a minimum attenuation in the 9-10 micrometers region. Fibers with an attenuation of less than 0.5 dB/m have been repeatly obtained. These fibers are coated with a UV curable or thermal plastic, in order to improve their mechanical properites. The IR remote spectroscopy using TeX fibers is one of the most promising applications. This technology allows to perform in situ, real-time, and on-line analysis of chemical and biological compounds. The study of industrial processes such as fermentations has been performed by this method, based on the use of these IR TeX fibers.

  18. Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy

    PubMed Central

    Nishida, Jun; Tamimi, Amr; Fei, Honghan; Pullen, Sonja; Ott, Sascha; Cohen, Seth M.; Fayer, Michael D.

    2014-01-01

    The structural elasticity of metal–organic frameworks (MOFs) is a key property for their functionality. Here, we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Methodology advances were required to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer. PMID:25512539

  19. Near-IR Spectroscopy of CEMP Stars with SOAR/OSIRIS

    NASA Astrophysics Data System (ADS)

    Kennedy, Catherine R.; Sivarani, Thirupathi; Beers, Timothy C.; Rossi, Silvia; Placco, Vinicius M.; Johnson, J.; Masseron, T.

    2010-03-01

    We report on medium-resolution near-IR spectroscopy of a sample of over 60 Carbon-Enhanced Metal-Poor (CEMP) stars observed with SOAR/OSIRIS, selected from the HK survey of Beers and colleagues and the Hamburg/ESO Survey of Christlieb and colleagues. Oxygen abundances from the molecular CO lines as well as rough estimates of 12C/13C ratios are estimated from the near-IR spectra of these stars. Near-IR model spectra with varying oxygen abundances, in combination with previously determined parameters from optical spectra are used for the estimation of abundances for this sample. As both oxygen abundances and 12C/13C ratios are tracers of nucleosynthesis, we hope to gain information about Galactic nucleosynthesis through the analysis of this sample.

  20. Hydrogen Bond Migration between Molecular Sites Observed with Ultrafast 2D IR Chemical Exchange Spectroscopy

    PubMed Central

    Rosenfeld, Daniel E.; Kwak, Kyungwon; Gengeliczki, Zsolt

    2010-01-01

    Hydrogen bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps, and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other non-migration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems. PMID:20121275

  1. Near-IR Fourier transform Raman spectroscopy in surgery and medicine: ophthalmic applications

    NASA Astrophysics Data System (ADS)

    Nie, Shuming; Yu, Nai-Teng; Ren, Qiushi

    1992-08-01

    This report describes the application of a recently developed spectroscopic technique, near- infrared-excited Fourier transform Raman scattering (abbreviated as near-IR FT-Raman) in the molecular-level characterization of normal and pathological human ocular tissues. The near-IR FT-Raman technique was shown to be particularly well-suited for the noninvasive analysis of intact ophthalmic samples because it exhibits such attractive features as complete fluorescence elimination, great sampling flexibility, high data acquisition speed, and measurement accuracy. For both intact human lenses and corneas, systematic FT-Raman studies were carried out in order to probe detailed molecular changes involved in cataract formation and cornea diseases. FT-Raman measurement was also made for synthetic biomaterials that can be attached to the corneal surface for laser refractive surgery. The technique of near-IR FT- Raman spectroscopy is potentially a nondestructive, non-invasive fingerprinting modality for monitoring lens aging, cataract formation, and corneal disease development.

  2. Particular features of the application of IR reflection spectroscopy methods in studies in archeology and paleontology

    NASA Astrophysics Data System (ADS)

    Zolotarev, V. M.; Khlopachev, G. A.

    2013-06-01

    We have considered an optical model of a porous rough surface with optical properties of objects (bone, flint) that are typical of archeology and paleontology. We have formulated an approach that makes it possible to perform mathematical processing of the IR reflection spectra of objects of this kind using standard algorithms and determine criteria that ensure obtaining reliable information on objects with a rough surface in the course of interpretation of frequencies in their IR reflection spectra. The potential of the approach has been demonstrated using as an example an investigation by the IR Fourier-transform reflection spectroscopy of mineralization processes of mammoth tusks from two paleolithic sites (14000 and 16000 BCE) located by the town of Yudinovo, Bryansk oblast, Russia.

  3. A salt-bridge structure in solution revealed by 2D-IR spectroscopy.

    PubMed

    Huerta-Viga, Adriana; Domingos, Sérgio R; Amirjalayer, Saeed; Woutersen, Sander

    2014-08-14

    Salt bridges are important interactions for the stability of protein conformations, but up to now it has been difficult to determine salt-bridge geometries in solution. Here we characterize the spatial structure of a salt bridge between guanidinium (Gdm(+)) and acetate (Ac(-)) using two-dimensional vibrational (2D-IR) spectroscopy. We find that as a result of salt bridge formation there is a significant change in the infrared response of Gdm(+) and Ac(-), and cross peaks between them appear in the 2D-IR spectrum. From the 2D-IR spectrum we determine the relative orientation of the transition-dipole moments of the vibrational modes of Gdm(+) and Ac(-), as well as the coupling between them. PMID:24676430

  4. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

    SciTech Connect

    Erikat, I. A.; Hamad, B. A.

    2013-11-07

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

  5. Simultaneous quantification of verbenalin and verbascoside in Verbena officinalis by ATR-IR and NIR spectroscopy.

    PubMed

    Schönbichler, S A; Bittner, L K H; Pallua, J D; Popp, M; Abel, G; Bonn, G K; Huck, C W

    2013-10-01

    Attenuated-total-reflectance infrared spectroscopy (ATR-IR) and near-infrared diffuse reflectance spectroscopy (NIR) in hyphenation with multivariate analysis was utilized to quantify verbenalin and verbascoside in Verbena officinalis. A new high performance liquid chromatography (HPLC) method as a reference was established and validated. For both vibrational spectroscopic methods test-set and cross validation were performed. Different data-pre-treatments like SNV, 1st and 2nd derivative were applied to remove systematic errors and were evaluated. Quality parameters obtained for the test-set validation revealed that ATR-IR (verbenalin: R(2)=0.94, RPD=4.23; verbascoside: R(2)=0.93, RPD=3.63) has advantages over NIR (verbenalin: R(2)=0.91, RPD=3.75; verbascoside: R(2)=0.80, RPD=2.35) in the given application. PMID:23810849

  6. Rapid detection of talcum powder in tea using FT-IR spectroscopy coupled with chemometrics.

    PubMed

    Li, Xiaoli; Zhang, Yuying; He, Yong

    2016-01-01

    This paper investigated the feasibility of Fourier transform infrared transmission (FT-IR) spectroscopy to detect talcum powder illegally added in tea based on chemometric methods. Firstly, 210 samples of tea powder with 13 dose levels of talcum powder were prepared for FT-IR spectra acquirement. In order to highlight the slight variations in FT-IR spectra, smoothing, normalize and standard normal variate (SNV) were employed to preprocess the raw spectra. Among them, SNV preprocessing had the best performance with high correlation of prediction (RP = 0.948) and low root mean square error of prediction (RMSEP = 0.108) of partial least squares (PLS) model. Then 18 characteristic wavenumbers were selected based on a hybrid of backward interval partial least squares (biPLS) regression, competitive adaptive reweighted sampling (CARS) algorithm and successive projections algorithm (SPA). These characteristic wavenumbers only accounted for 0.64% of the full wavenumbers. Following that, 18 characteristic wavenumbers were used to build linear and nonlinear determination models by PLS regression and extreme learning machine (ELM), respectively. The optimal model with RP = 0.963 and RMSEP = 0.137 was achieved by ELM algorithm. These results demonstrated that FT-IR spectroscopy with chemometrics could be used successfully to detect talcum powder in tea. PMID:27468701

  7. Rapid detection of talcum powder in tea using FT-IR spectroscopy coupled with chemometrics

    PubMed Central

    Li, Xiaoli; Zhang, Yuying; He, Yong

    2016-01-01

    This paper investigated the feasibility of Fourier transform infrared transmission (FT-IR) spectroscopy to detect talcum powder illegally added in tea based on chemometric methods. Firstly, 210 samples of tea powder with 13 dose levels of talcum powder were prepared for FT-IR spectra acquirement. In order to highlight the slight variations in FT-IR spectra, smoothing, normalize and standard normal variate (SNV) were employed to preprocess the raw spectra. Among them, SNV preprocessing had the best performance with high correlation of prediction (RP = 0.948) and low root mean square error of prediction (RMSEP = 0.108) of partial least squares (PLS) model. Then 18 characteristic wavenumbers were selected based on a hybrid of backward interval partial least squares (biPLS) regression, competitive adaptive reweighted sampling (CARS) algorithm and successive projections algorithm (SPA). These characteristic wavenumbers only accounted for 0.64% of the full wavenumbers. Following that, 18 characteristic wavenumbers were used to build linear and nonlinear determination models by PLS regression and extreme learning machine (ELM), respectively. The optimal model with RP = 0.963 and RMSEP = 0.137 was achieved by ELM algorithm. These results demonstrated that FT-IR spectroscopy with chemometrics could be used successfully to detect talcum powder in tea. PMID:27468701

  8. Investigation of bis-crown ethers for ion-selective electrodes by FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Egyed, O.; Izvekov, V. P.; Toth, K.; Holly, S.; Pungor, E.

    1990-03-01

    The structure of bis-benzo-15-crown-5 derivatives containing nitro groups and urethane linkages has been studied by FT-IR spectroscopy, regarding especially the secondary bonds (H-bridges) of the chain connecting the two crow rings of the molecule. It was concluded that the formation of an ion trap stabilized by intramolecular cross H-bonds between urethane NH groups and O atoms is presumable.

  9. Breath air measurement using wide-band frequency tuning IR laser photo-acoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Kistenev, Yury V.; Borisov, Alexey V.; Kuzmin, Dmitry A.; Bulanova, Anna A.; Boyko, Andrey A.; Kostyukova, Nadezhda Y.; Karapuzikov, Alexey A.

    2016-03-01

    The results of measuring of biomarkers in breath air of patients with broncho-pulmonary diseases using wide-band frequency tuning IR laser photo-acoustic spectroscopy and the methods of data mining are presented. We will discuss experimental equipment and various methods of intellectual analysis of the experimental spectra in context of above task. The work was carried out with partial financial support of the FCPIR contract No 14.578.21.0082 (ID RFMEFI57814X0082).

  10. Practical Analysis of materials with depth varying compositions using FT-IR photoacoustic spectroscopy (PAS)

    SciTech Connect

    J.F. McClelland; R.W. Jones; Siquan Luo

    2004-09-30

    FT-IR photoacoustic spectroscopy (PAS) is discussed as a nondestructive method to probe the molecular composition of materials versus depth on the basis of the analysis of layers of experimentally controllable thickness, which are measured from the sample surface to depths of some tens of micrometers, depending on optical and thermal properties. Computational methods are described to process photoacoustic amplitude and phase spectra for both semi-quantitative and quantitative depth analyses. These methods are demonstrated on layered and gradient samples.

  11. X-ray absorption spectroscopy of bacterial sulfur globules

    SciTech Connect

    George, Graham N.

    2002-08-01

    Sulfur K-edge X-ray absorption spectroscopy is a powerful in situ probe of sulfur biochemistry in intact cells and tissues. Under favorable circumstances the technique can provide quantitative information on the chemical identify of the sulfur species that are present in a sample. Prange et al. have recently reported an X-ray absorption spectroscopic study of bacterial sulfur storage globules. Unfortunately there are substantial problems with the experimental technique employed that, they contend, lead to completely erroneous conclusions. In the more recent of their two papers Prange et al. employed a curve-fitting method similar to that used by us (for more than 10 years). In essence, the method employs simply fitting a linear combination of the spectra of standard compounds to that of the unknown, in this case cultures of bacterial cells. This type of analysis can provide quantitative estimates of the individual sulfur types in the sample, but is critically dependent upon the choice of reference spectra. Prange et al. deduce substantial differences between the chemical forms of sulfur stored in the globules of different organisms; they conclude that the globules of Beggiatoa alba and Thiomargarita namibiensis contain cyclo-octasulfur (S{sub 8}), while those of other organisms contain polythionates (Acidithiobacillus ferrooxidans) and polymeric sulfur (e.g. Allochromatium vinosum). This is in contradiction with an earlier study, in which they found that sulfur in all globule species examined resembled that expected for various sized spherical particles of S{sub 8}. The discrepancy is due to an experimental artefact in the work of Prange et al. arising from their choice of transmittance detection, which is also discussed.

  12. A novel algorithm to attack the problem of pattern recognition with near-IR spectroscopy

    SciTech Connect

    Zou, Yi.

    1993-01-01

    Near-infrared (near-IR) spectroscopy is a rapid, nondestructive analytical technique that has wide application in industry as well as in academic research. In general, near-IR analysis uses reflectance or absorbance signals to determine chemical information from samples. Near-IR is also a very good technique for differentiating samples from different sources using pattern recognition analysis. In this dissertation, a novel algorithm of the quantile BEST (Boot-strap Error-adjusted Sample Technique) for pattern recognition analysis has been extensively tested with hypothetical data and real samples. A modified model is proposed to improve the system performance in higher dimensional space. The applications to real samples include: (1) the identification of the points of origin of soil samples; (2) near-IR spectrophotometric monitoring of stroke-related changes in the protein and lipid composition of whole gerbil brains; and (3) determination of cholesterol concentration in aqueous and serum samples with principal component analysis. In addition, a new laser spectroscopic system is designed and tested. This system uses Nd-YAG and dye lasers are primary sources. Powerful near-IR radiation is obtained from stimulated Raman scattering. The stability, accuracy, and precision of the system is investigated and an application to known samples is shown.

  13. IR double-resonance spectroscopy applied to the 4-aminophenol(H2O)1 cluster

    NASA Astrophysics Data System (ADS)

    Gerhards, M.; Unterberg, C.

    2001-04-01

    The IR double-resonance techniques IR/R2PI (infrared/resonant 2-photon ionization), IR/PIRI (infrared-photo-induced Rydberg ionization) and IR-photodissociation spectroscopy are valuable tools to investigate structure, vibrations, and dynamical processes of neutral and ionic hydrogen-bonded clusters containing aromatic molecules. In this paper we report on the application of the IR double-resonance techniques to determine the NH and OH stretching vibrations of 4-aminophenol and 4-aminophenol(H2O)1, both in the neutral (S0) and ionic (D0) ground state. All vibrational frequencies obtained for 4-aminophenol and the cluster are compared with the values obtained from ab initio and DFT calculations. In the S0 state, a trans-linear arrangement of 4-aminophenol(H2O)1 is obtained containing an O-H..O hydrogen bond. In the D0 state an overlay of two spectra can be observed resulting from the trans-linear structure and a second structure which contains a N-H..O hydrogen bond. The observation of these two structures within the ion is an interesting example of a rearrangement reaction in the ionic state.

  14. Cavity-Enhanced Absorption Spectroscopy and Photoacoustic Spectroscopy for Human Breath Analysis

    NASA Astrophysics Data System (ADS)

    Wojtas, J.; Tittel, F. K.; Stacewicz, T.; Bielecki, Z.; Lewicki, R.; Mikolajczyk, J.; Nowakowski, M.; Szabra, D.; Stefanski, P.; Tarka, J.

    2014-12-01

    This paper describes two different optoelectronic detection techniques: cavity-enhanced absorption spectroscopy and photoacoustic spectroscopy. These techniques are designed to perform a sensitive analysis of trace gas species in exhaled human breath for medical applications. With such systems, the detection of pathogenic changes at the molecular level can be achieved. The presence of certain gases (biomarkers), at increased concentration levels, indicates numerous human diseases. Diagnosis of a disease in its early stage would significantly increase chances for effective therapy. Non-invasive, real-time measurements, and high sensitivity and selectivity, capable of minimum discomfort for patients, are the main advantages of human breath analysis. At present, monitoring of volatile biomarkers in breath is commonly useful for diagnostic screening, treatment for specific conditions, therapy monitoring, control of exogenous gases (such as bacterial and poisonous emissions), as well as for analysis of metabolic gases.

  15. Absorption and emission spectroscopy of individual semiconductor nanostructures

    NASA Astrophysics Data System (ADS)

    McDonald, Matthew P.

    The advent of controllable synthetic methods for the production of semiconductor nanostructures has led to their use in a host of applications, including light-emitting diodes, field effect transistors, sensors, and even television displays. This is, in part, due to the size, shape, and morphologically dependent optical and electrical properties that make this class of materials extremely customizable; wire-, rod- and sphere-shaped nanocrystals are readily synthesized through common wet chemical methods. Most notably, confining the physical dimension of the nanostructure to a size below its Bohr radius (aB) results in quantum confinement effects that increase its optical energy gap. Not only the size, but the shape of a particle can be exploited to tailor its optical and electrical properties. For example, confined CdSe quantum dots (QDs) and nanowires (NWs) of equivalent diameter possess significantly different optical gaps. This phenomenon has been ascribed to electrostatic contributions arising from dielectric screening effects that are more pronounced in an elongated (wire-like) morphology. Semiconducting nanostructures have thus received significant attention over the past two decades. However, surprisingly little work has been done to elucidate their basic photophysics on a single particle basis. What has been done has generally been accomplished through emission-based measurements, and thus does not fully capture the full breadth of these intriguing systems. What is therefore needed then are absorption-based studies that probe the size and shape dependent evolution of nanostructure photophysics. This thesis summarizes the single particle absorption spectroscopy that we have carried out to fill this knowledge gap. Specifically, the diameter-dependent progression of one-dimensional (1D) excitonic states in CdSe NWs has been revealed. This is followed by a study that focuses on the polarization selection rules of 1D excitons within single CdSe NWs. Finally

  16. Polarization shaping in the mid-IR and polarization-based balanced heterodyne detection with application to 2D IR spectroscopy

    PubMed Central

    Middleton, Chris T.; Strasfeld, David B.; Zanni, Martin T.

    2010-01-01

    We demonstrate amplitude, phase and polarization shaping of femtosecond mid-IR pulses using a germanium acousto-optical modulator by independently shaping the frequency-dependent amplitudes and phases of two orthogonally polarized pulses which are then collinearly overlapped using a wire-grid polarizer. We use a feedback loop to set and stabilize the relative phase of the orthogonal pulses. We have also used a wire-grid polarizer to implement polarization-based balanced heterodyne detection for improved signal-to-noise of 2D IR spectra collected in a pump-probe geometry. Applications include coherent control of molecular vibrations and improvements in multidimensional IR spectroscopy. PMID:19687931

  17. Differentiation of the root of Cultivated Ginseng, Mountain Cultivated Ginseng and Mountain Wild Ginseng using FT-IR and two-dimensional correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Dan; Li, Yong-Guo; Xu, Hong; Sun, Su-Qin; Wang, Zheng-Tao

    2008-07-01

    Ginseng is one of the most widely used herbal medicines. Based on the grown environments and the cultivate method, three kinds of ginseng, Cultivated Ginseng (CG), Mountain Cultivated Ginseng (MCG) and Mountain Wild Ginseng (MWG) are classified. A novel and scientific-oriented method was developed and established to discriminate and identify three kinds of ginseng using Fourier transform infrared spectroscopy (FT-IR), secondary derivative IR spectra and two-dimensional correlation infrared spectroscopy (2D-IR). The findings indicated that the relative contents of starch in the CG were more than that in MCG and MWG, while the relative contents of calcium oxalate and lipids in MWG were more than that in CG and MCG, and the relative contents of fatty acid in MCG were more than that in CG and MWG. The hierarchical cluster analysis was applied to data analysis of MWG, CG and MWG, which could be classified successfully. The results demonstrated the macroscopic IR fingerprint method, including FT-IR, secondary derivative IR and 2D-IR, can be applied to discriminate different ginsengs rapidly, effectively and non-destructively.

  18. X-Ray Absorption Spectroscopy Imaging of Biological Tissues

    NASA Astrophysics Data System (ADS)

    Pickering, Ingrid J.; George, Graham N.

    2007-02-01

    X-ray absorption spectroscopy (XAS) is proving invaluable in determining the average chemical form of metals or metalloids in intact biological tissues. As most tissues have spatial structure, there is great additional interest in visualizing the spatial location of the metal(loid) as well as its chemical forms. XAS imaging gives the opportunity of producing maps of specific chemical types of elements in vivo in dilute biological systems. X-ray fluorescence microprobe techniques are routinely used to study samples with spatial heterogeneity. Microprobe produces elemental maps, with chemical sensitivity obtained by recording micro-XAS spectra at selected point locations on the map. Unfortunately, using these procedures spatial detail may be lost as the number of point spectra recorded generally is limited. A powerful extension of microprobe is XAS imaging or chemically specific imaging. Here, the incident energy is tuned to features in the near-edge which are characteristic of the expected chemical forms of the element. With a few simple assumptions, these XAS images can then be converted to quantitative images of specific chemical form, yielding considerable clarity in the distributions.

  19. X-Ray Absorption Spectroscopy of Dinuclear Metallohydrolases

    PubMed Central

    Tierney, David L.; Schenk, Gerhard

    2014-01-01

    In this mini-review, we briefly discuss the physical origin of x-ray absorption spectroscopy (XAS) before illustrating its application using dinuclear metallohydrolases as exemplary systems. The systems we have selected for illustrative purposes present a challenging problem for XAS, one that is ideal to demonstrate the potential of this methodology for structure/function studies of metalloenzymes in general. When the metal ion is redox active, XAS provides a sensitive measure of oxidation-state-dependent differences. When the metal ion is zinc, XAS is the only spectroscopic method that will provide easily accessible structural information in solution. In the case of heterodimetallic sites, XAS has the unique ability to interrogate each metal site independently in the same sample. One of the strongest advantages of XAS is its ability to examine metal ion site structures with crystallographic precision, without the need for a crystal. This is key for studying flexible metal ion sites, such as those described in the selected examples, because it allows one to monitor structural changes that occur during substrate turnover. PMID:25229134

  20. X-ray Absorption Spectroscopy of the Rare Earth orthophosphates

    SciTech Connect

    Shuh, D.K.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-06-01

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d{sup 10}4f{sup n} {yields} 3d-{sup 9}4f{sup n+1} transitions and these transitions exhibit a wealth of spectroscopic features. The XAS measurements of single crystal REPO{sub 4} (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) at the 3d edge were performed in the total yield mode at beam line 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble the XAS of the corresponding RE metal. This is not unexpected and emphasizes the major contribution of the trivalent state to the electronic transitions at the RE 3d edges. These spectra unequivocally identify the transitions originating from well-characterized RE cores and correlate well with previous theoretical investigations.

  1. Decay Heat Measurements Using Total Absorption Gamma-ray Spectroscopy

    NASA Astrophysics Data System (ADS)

    Rice, S.; Valencia, E.; Algora, A.; Taín, J. L.; Regan, P. H.; Podolyák, Z.; Agramunt, J.; Gelletly, W.; Nichols, A. L.

    2012-09-01

    A knowledge of the decay heat emitted by thermal neutron-irradiated nuclear fuel is an important factor in ensuring safe reactor design and operation, spent fuel removal from the core, and subsequent storage prior to and after reprocessing, and waste disposal. Decay heat can be readily calculated from the nuclear decay properties of the fission products, actinides and their decay products as generated within the irradiated fuel. Much of the information comes from experiments performed with HPGe detectors, which often underestimate the beta feeding to states at high excitation energies. This inability to detect high-energy gamma emissions effectively results in the derivation of decay schemes that suffer from the pandemonium effect, although such a serious problem can be avoided through application of total absorption γ-ray spectroscopy (TAS). The beta decay of key radionuclei produced as a consequence of the neutron-induced fission of 235U and 239Pu are being re-assessed by means of this spectroscopic technique. A brief synopsis is given of the Valencia-Surrey (BaF2) TAS detector, and their method of operation, calibration and spectral analysis.

  2. [Measurements of IR absorption across section and spectrum simulation of lewisite].

    PubMed

    Zhang, Yuan-peng; Wang, Hai-tao; Zhang, Lin; Yang, Liu; Guo, Xiao-di; Bai, Yun; Sun, Hao

    2015-02-01

    The vapor infrared transmission spectra of varied concentration of lewisite-1 were measured by a long-path FT-IR spectrometer, and its characteristic frequencies are 814, 930, 1563 cm(-1); their infrared absorption cross section (a) were determined using Beer-Lambert law. The corresponding sigma values are 3.89 +/- 0.01, 1.43 +/- 0.06, 4.47 +/- 0.05 ( X 10(-20) cm2 x molecule(-1)). Two little teeny peaks, 1158, 1288 cm(-1) were found in the measured spectra. Density Functional Theory (DFT) was applied to calculated the infrared spectra of lewisite-1, -2, -3 on a b3lyp/6-311+g(d, p) level by Gauss09 package. The vibration modes were assigned by Gaussview5. 08. The calculated spectra and experimental spectra are in good agreement with each other in 600-1600 cm(-1) range, for the Person's r is 0.9991. The calculated spectra also showed three characteristic frequencies (293, 360, 374 cm(-1)) related to As atom. 0.977 was a scaling factor we determined for lewisite-1 through least-square error and its performance to scale lewisite-1, -2, -3 was acceptable. The results of this work are useful for monitoring environmental atmospheric concentrations of lewisite. PMID:25970914

  3. Intracavity Dye-Laser Absorption Spectroscopy (IDLAS) for application to planetary molecules

    NASA Technical Reports Server (NTRS)

    Lang, Todd M.; Allen, John E., Jr.

    1990-01-01

    Time-resolved, quasi-continuous wave, intracavity dye-laser absorption spectroscopy is applied to the investigation of absolute absorption coefficients for vibrational-rotational overtone bands of water at visible wavelengths. Emphasis is placed on critical factors affecting detection sensitivity and data analysis. Typical generation-time dependent absorption spectra are given.

  4. Monitoring lipase-catalyzed interesterification for bulky fat modification with FT-IR/NIR spectroscopy.

    PubMed

    Chang, Tinghong; Lai, Xuxin; Zhang, Hong; Søndergaard, Ib; Xu, Xuebing

    2005-12-28

    This work demonstrates the application of FT-IR and FT-NIR spectroscopy to monitor the enzymatic interesterification process for bulky fat modification. The reaction was conducted between palm stearin and coconut oil (70:30, w/w) with the catalysis of Lipozyme TL IM at 70 degrees C in a batch reactor. The blends and interesterified fat samples in liquid form were measured by attenuated total reflectance based FT-IR (spectra region, 1516-781 cm(-1)) and transmission mode based FT-NIR (spectra region, 5369-4752 cm(-1)) with the temperature of both controlled at 70 degrees C. The samples in solid form were also measured by reflectance-based FT-NIR (spectra regions, 7037-6039 and 5995-5612 cm(-1)) at room temperature. Calibrations of FT-IR and FT-NIR for conversion degrees (evaluated by triglyceride profile), solid fat contents (SFC), and dropping points of interesterified products were carried out by using partial least-squares regression. High correlations (r > 0.96) were obtained from cross validations of the data estimated by FT-IR, FT-NIR, and the above-mentioned conventional analytical methods, except for correlations (r = 0.90-0.95) between FT-IR and SFC profiles. Overall, FT-NIR spectroscopy coupled with transmission mode measured at 70 degrees C had the highest correlations, which also had the closest conditions to the sampled products in the process, indicating a great potential for implementation as an on-line control for monitoring the enzymatic interesterification process. PMID:16366664

  5. Study on antibacterial alginate-stabilized copper nanoparticles by FT-IR and 2D-IR correlation spectroscopy

    PubMed Central

    Díaz-Visurraga, Judith; Daza, Carla; Pozo, Claudio; Becerra, Abraham; von Plessing, Carlos; García, Apolinaria

    2012-01-01

    Background The objective of this study was to clarify the intermolecular interaction between antibacterial copper nanoparticles (Cu NPs) and sodium alginate (NaAlg) by Fourier transform infrared spectroscopy (FT-IR) and to process the spectra applying two-dimensional infrared (2D-IR) correlation analysis. To our knowledge, the addition of NaAlg as a stabilizer of copper nanoparticles has not been previously reported. It is expected that the obtained results will provide valuable additional information on: (1) the influence of reducing agent ratio on the formation of copper nanoparticles in order to design functional nanomaterials with increased antibacterial activity, and (2) structural changes related to the incorporation of Cu NPs into the polymer matrix. Methods Cu NPs were prepared by microwave heating using ascorbic acid as reducing agent and NaAlg as stabilizing agent. The characterization of synthesized Cu NPs by ultraviolet visible spectroscopy, transmission electron microscopy (TEM), electron diffraction analysis, X-ray diffraction (XRD), and semiquantitative analysis of the weight percentage composition indicated that the average particle sizes of Cu NPs are about 3–10 nm, they are spherical in shape, and consist of zerovalent Cu and Cu2O. Also, crystallite size and relative particle size of stabilized Cu NPs were calculated by XRD using Scherrer’s formula and FT from the X-ray diffraction data. Thermogravimetric analysis, differential thermal analysis, differential scanning calorimetry (DSC), FT-IR, second-derivative spectra, and 2D-IR correlation analysis were applied to studying the stabilization mechanism of Cu NPs by NaAlg molecules. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of stabilized Cu NPs against five bacterial strains (Staphylococccus aureus ATCC 6538P, Escherichia coli ATCC 25922 and O157: H7, and Salmonella enterica serovar Typhimurium ATCC 13311 and 14028) were evaluated with macrodilution

  6. Potential of mid IR spectroscopy in the rapid label free identification of skin malignancies

    NASA Astrophysics Data System (ADS)

    Kastl, Lena; Kemper, Björn; Lloyd, Gavin R.; Nallala, Jayakrupakar; Stone, Nick; Naranjo, Valery; Penaranda, Francisco; Schnekenburger, Jürgen

    2016-03-01

    The rapid inspection of suspicious skin lesions for pathological cell types is the objective of optical point of care diagnostics technologies. A marker free fast diagnosis of skin malignancies would overcome the limitations of the current gold standard surgical biopsy. The time consuming and costly biopsy procedure requires the inspection of each sample by a trained pathologist, which limits the analysis of potentially malignant lesions. Optical technologies like RAMAN or infrared spectroscopy, which provide both, localization and chemical information, can be used to differentiate malignant from healthy tissue by the analysis of multi cell structures and cell type specific spectra. We here report the application of midIR spectroscopy towards fast and reliable skin diagnostics. Within the European research project MINERVA we developed standardized in vitro skin systems with increasing complexity, from single skin cell types as fibroblasts, keratinocytes and melanoma cells, to mixtures of these and finally three dimensional human skin equivalents. The standards were characterized in the established midIR range and also with newly developed systems for fast imaging up to 12 μm. The analysis of the spectra by novel data processing algorithms demonstrated the clear separation of all cell types, especially the tumor cells. The signals from single cell layers were sufficient for cell type differentiation. We have compared different midIR systems and found all of them suitable for specific cell type identification. Our data demonstrate the potential of midIR spectroscopy for fast image acquisition and an improved data processing as sensitive and specific optical biopsy technology.

  7. Mid-IR near-perfect absorption with a SiC photonic crystal with angle-controlled polarization selectivity.

    PubMed

    Devarapu, G C R; Foteinopoulou, S

    2012-06-01

    We theoretically investigate mid-IR absorption enhancement with a SiC one-dimensional photonic crystal (PC) microstructure at the frequency regime of the phonon-polariton band gap, where efficient absorption is unattainable in the bulk material. Our study reveals an intricate relationship between absorption efficiency and the energy velocity of light propagation, that is far more complex than hitherto believed. In particular, our findings suggest that absorption peaks away from the photonic-crystal band edge where energy velocity is minimum. While efficient absorption is still associated with a slow-light mode, the latter is faster by at least an order of magnitude in comparison to the bulk material. Moreover, our calculations suggest that absorption becomes optimal when light gradually slow downs as it enters the PC. Relying on this insight, we achieved near-perfect absorption around the phonon-polariton mid-gap frequency with a PC with a suitably terminated end face. We further demonstrate that the near-perfect absorptive property can be tuned with the incident light angle, to be polarization insensitive or polarization selective. We believe our proposed non-metallic paradigm opens up a new route for harnessing infrared absorption with semiconductor and ionic-crystal materials. PMID:22714331

  8. Identification and characterization of salmonella serotypes using DNA spectral characteristics by fourier transform infrared (FT-IR) spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analysis of DNA samples of Salmonella serotypes (Salmonella Typhimurium, Salmonella Enteritidis, Salmonella Infantis, Salmonella Heidelberg and Salmonella Kentucky) were performed using Fourier transform infrared spectroscopy (FT-IR) spectrometer by placing directly in contact with a diamond attenua...

  9. The importance of correcting for variable probe-sample interactions in AFM-IR spectroscopy: AFM-IR of dried bacteria on a polyurethane film.

    PubMed

    Barlow, Daniel E; Biffinger, Justin C; Cockrell-Zugell, Allison L; Lo, Michael; Kjoller, Kevin; Cook, Debra; Lee, Woo Kyung; Pehrsson, Pehr E; Crookes-Goodson, Wendy J; Hung, Chia-Suei; Nadeau, Lloyd J; Russell, John N

    2016-08-01

    AFM-IR is a combined atomic force microscopy-infrared spectroscopy method that shows promise for nanoscale chemical characterization of biological-materials interactions. In an effort to apply this method to quantitatively probe mechanisms of microbiologically induced polyurethane degradation, we have investigated monolayer clusters of ∼200 nm thick Pseudomonas protegens Pf-5 bacteria (Pf) on a 300 nm thick polyether-polyurethane (PU) film. Here, the impact of the different biological and polymer mechanical properties on the thermomechanical AFM-IR detection mechanism was first assessed without the additional complication of polymer degradation. AFM-IR spectra of Pf and PU were compared with FTIR and showed good agreement. Local AFM-IR spectra of Pf on PU (Pf-PU) exhibited bands from both constituents, showing that AFM-IR is sensitive to chemical composition both at and below the surface. One distinct difference in local AFM-IR spectra on Pf-PU was an anomalous ∼4× increase in IR peak intensities for the probe in contact with Pf versus PU. This was attributed to differences in probe-sample interactions. In particular, significantly higher cantilever damping was observed for probe contact with PU, with a ∼10× smaller Q factor. AFM-IR chemical mapping at single wavelengths was also affected. We demonstrate ratioing of mapping data for chemical analysis as a simple method to cancel the extreme effects of the variable probe-sample interactions. PMID:27403761

  10. Earle K. Plyler Prize for Molecular Spectroscopy and Dynamics Lecture: 2D IR Spectroscopy of Peptide Conformation

    NASA Astrophysics Data System (ADS)

    Tokmakoff, Andrei

    2012-02-01

    Descriptions of protein and peptide conformation are colored by the methods we use to study them. Protein x-ray and NMR structures often lead to impressions of rigid or well-defined conformations, even though these are dynamic molecules. The conformational fluctuations and disorder of proteins and peptides is more difficult to quantify. This presentation will describe an approach toward characterizing and quantifying structural heterogeneity and disorder in peptides using 2D IR spectroscopy. Using amide I vibrational spectroscopy, isotope labeling strategies, and computational modeling based on molecular dynamics simulations and Markov state models allows us to characterize distinct peptide conformers and conformational variation. The examples illustrated include the beta-hairpin tripzip2 and elastin-like peptides.

  11. Collaborative Student Laboratory Exercise Using FT-IR Spectroscopy for the Kinetics Study of a Biotin Analogue

    ERIC Educational Resources Information Center

    Leong, Jhaque; Ackroyd, Nathan C.; Ho, Karen

    2014-01-01

    The synthesis of N-methoxycarbonyl-2-imidazolidone, an analogue of biotin, was conducted by organic chemistry students and confirmed using FT-IR and H NMR. Spectroscopy students used FT-IR to measure the rate of hydrolysis of the product and determined the rate constant for the reaction using the integrated rate law. From the magnitude of the rate…

  12. Measurement of atmospheric oxygen concentration by near-infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hoffnagle, J.

    2013-12-01

    Variations in the concentration of molecular oxygen in the atmosphere have been shown to provide important constraints on the global carbon dioxide budget (1). Numerous technologies have been explored to measure oxygen concentration, including detection of paramagnetism, gas chromatography, fuel cells, mass spectroscopy, interferometry, and absorption spectroscopy from the UV to IR. Geophysical applications impose severe demands on the precision of an oxygen concentration sensor. Oxygen variations are conventionally expressed using the delta notation applied to the O2/N2 ratio; a change of approximately 5 per meg in delta corresponds to a 1 ppm change in the atmospheric mole fraction of oxygen. Because of the large resevoir of oxygen in the atmosphere, variations of oxygen concentration are small and measurement precision on the order of several per meg is needed to extract geophysically useful information. We describe an instrument that determines the oxygen content of an atmospheric sample by using wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) to measure an absorption line in the 1.2 micron band of the oxygen molecule. The CRDS method provides very high precision measurements of the optical absorption coefficient, better than 0.1 ppb/cm in 1 s measurement time, and large dynamic range. The sample temperature and pressure are stabilized to better than 5 mK and 2 Pa, respectively. The precision of the oxygen concentration measurement was characterized by the Allan variance of repeated measurements of a tank of dry air. For a 5 minute averaging period, the Allan variance of the concentration was 1 ppm. Moreover, the Allan variance continued to decline for longer time scales, reaching 0.4 ppm (corresponding to 2 per meg in delta of O2/N2) after one hour. This work demonstrates the possibility of spectroscopic measurement of molecular oxygen concentration with high precision on the time scale of minutes and good long term stability. 1. R. F. Keeling and S

  13. Apoptosis-induced structural changes in leukemia cells identified by IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, K.-Z.; Mantsch, H. H.

    2001-05-01

    Apoptotic changes induced in the leukemia cell line CEM by treatment with the chemical etoposide were investigated by IR spectroscopy. Characteristic band alterations were identified in the apoptotic cells arising from cellular protein, lipid and DNA. Besides general changes such as an increase in lipid content and a decrease in the amount of detectable DNA, there were specific changes that affected the secondary structure of proteins in the apoptotic leukemia cells, i.e. the dominant protein structure shifts from β-sheet in the control cells to unordered coil in the apoptotic cells. The student's t-test was applied to the spectral range 1500-1700 cm -1 in order to determine the significant differences of protein structure between control and etoposide treated cells at various time points. A temporal relationship was found between the spectrally significant differences of the protein structure in the apoptotic cells and the severity of apoptosis. The IR spectral changes of protein structure also correlate well with the activity of caspase-3, an important proteolytic enzyme in apoptosis. This preliminary study suggests that IR spectroscopy could possibly be used to monitor and quantitate apoptosis in leukemia cells.

  14. Dye aggregation identified by vibrational coupling using 2D IR spectroscopy

    SciTech Connect

    Oudenhoven, Tracey A.; Laaser, Jennifer E.; Zanni, Martin T.; Joo, Yongho; Gopalan, Padma

    2015-06-07

    We report that a model dye, Re(CO){sub 3}(bypy)CO{sub 2}H, aggregates into clusters on TiO{sub 2} nanoparticles regardless of our preparation conditions. Using two-dimensional infrared (2D IR) spectroscopy, we have identified characteristic frequencies of monomers, dimers, and trimers. A comparison of 2D IR spectra in solution versus those deposited on TiO{sub 2} shows that the propensity to dimerize in solution leads to higher dimer formation on TiO{sub 2}, but that dimers are formed even if there are only monomers in solution. Aggregates cannot be washed off with standard protocols and are present even at submonolayer coverages. We observe cross peaks between aggregates of different sizes, primarily dimers and trimers, indicating that clusters consist of microdomains in close proximity. 2D IR spectroscopy is used to draw these conclusions from measurements of vibrational couplings, but if molecules are close enough to be vibrationally coupled, then they are also likely to be electronically coupled, which could alter charge transfer.

  15. Folding of a heterogeneous β-hairpin peptide from temperature-jump 2D IR spectroscopy

    PubMed Central

    Jones, Kevin C.; Peng, Chunte Sam; Tokmakoff, Andrei

    2013-01-01

    We provide a time- and structure-resolved characterization of the folding of the heterogeneous β-hairpin peptide Tryptophan Zipper 2 (Trpzip2) using 2D IR spectroscopy. The amide I′ vibrations of three Trpzip2 isotopologues are used as a local probe of the midstrand contacts, β-turn, and overall β-sheet content. Our experiments distinguish between a folded state with a type I′ β-turn and a misfolded state with a bulged turn, providing evidence for distinct conformations of the peptide backbone. Transient 2D IR spectroscopy at 45 °C following a laser temperature jump tracks the nanosecond and microsecond kinetics of unfolding and the exchange between conformers. Hydrogen bonds to the peptide backbone are loosened rapidly compared with the 5-ns temperature jump. Subsequently, all relaxation kinetics are characterized by an observed 1.2 ± 0.2-μs exponential. Our time-dependent 2D IR spectra are explained in terms of folding of either native or nonnative contacts from a common compact disordered state. Conversion from the disordered state to the folded state is consistent with a zip-out folding mechanism. PMID:23382249

  16. Electronic transitions and heterogeneity of the bacteriophytochrome Pr absorption band: An angle balanced polarization resolved femtosecond VIS pump–IR probe study

    PubMed Central

    Linke, Martin; Yang, Yang; Zienicke, Benjamin; Hammam, Mostafa A.S.; von Haimberger, Theodore; Zacarias, Angelica; Inomata, Katsuhiko; Lamparter, Tilman; Heyne, Karsten

    2013-01-01

    Photoisomerization of biliverdin (BV) chromophore triggers the photoresponse in native Agp1 bacteriophytochrome. We discuss heterogeneity in phytochrome Pr form to account for the shape of the absorption profile. We investigated different regions of the absorption profile by angle balanced polarization resolved femtosecond VIS pump–IR probe spectroscopy. We studied the Pr form of Agp1 with its natural chromophore and with a sterically locked 18Et-BV (locked Agp1). We followed the dynamics and orientations of the carbonyl stretching vibrations of ring D and ring A in their ground and electronically excited states. Photoisomerization of ring D is reflected by strong signals of the ring D carbonyl vibration. In contrast, orientational data on ring A show no rotation of ring A upon photoexcitation. Orientational data allow excluding a ZZZasa geometry and corroborates a nontwisted ZZZssa geometry of the chromophore. We found no proof for heterogeneity but identified a new, to our knowledge, electronic transition in the absorption profile at 644 nm (S0→S2). Excitation of the S0→S2 transition will introduce a more complex photodynamics compared with S0→S1 transition. Our approach provides fundamental information on disentanglement of absorption profiles, identification of chromophore structures, and determination of molecular groups involved in the photoisomerization process of photoreceptors. PMID:24138851

  17. Attenuated total reflectance-FT-IR spectroscopy for gunshot residue analysis: potential for ammunition determination.

    PubMed

    Bueno, Justin; Sikirzhytski, Vitali; Lednev, Igor K

    2013-08-01

    The ability to link a suspect to a particular shooting incident is a principal task for many forensic investigators. Here, we attempt to achieve this goal by analysis of gunshot residue (GSR) through the use of attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FT-IR) combined with statistical analysis. The firearm discharge process is analogous to a complex chemical process. Therefore, the products of this process (GSR) will vary based upon numerous factors, including the specific combination of the firearm and ammunition which was discharged. Differentiation of FT-IR data, collected from GSR particles originating from three different firearm-ammunition combinations (0.38 in., 0.40 in., and 9 mm calibers), was achieved using projection to latent structures discriminant analysis (PLS-DA). The technique was cross (leave-one-out), both internally and externally, validated. External validation was achieved via assignment (caliber identification) of unknown FT-IR spectra from unknown GSR particles. The results demonstrate great potential for ATR-FT-IR spectroscopic analysis of GSR for forensic purposes. PMID:23745950

  18. Compact large-aperture Fabry-Perot interferometer modules for gas spectroscopy at mid-IR

    NASA Astrophysics Data System (ADS)

    Kantojärvi, Uula; Varpula, Aapo; Antila, Tapani; Holmlund, Christer; Mäkynen, Jussi; Näsilä, Antti; Mannila, Rami; Rissanen, Anna; Antila, Jarkko; Disch, Rolf J.; Waldmann, Torsten A.

    2014-03-01

    VTT has developed Fabry-Pérot Interferometers (FPI) for visible and infrared wavelengths since 90's. Here we present two new platforms for mid-infrared gas spectroscopy having a large optical aperture to provide high optical throughput but still enabling miniaturized instrument size. First platform is a tunable filter that replaces a traditional filter wheel, which operates between wavelengths of 4-5 um. Second platform is for correlation spectroscopy where the interferometer provides a comb-like transmission pattern mimicking absorption of diatomic molecules at the wavelength range of 4.7-4.8 um. The Bragg mirrors have 2-4 thin layers of polysilicon and silicon oxide.

  19. IR reflectance spectroscopy of carbon dioxide clathrate hydrates. Implications for Saturn's icy moons.

    NASA Astrophysics Data System (ADS)

    Oancea, A.; Grasset, O.; Le Menn, E.; Bezacier, L.; Bollengier, O.; Le Mouélic, S.; Tobie, G.

    2012-04-01

    A CO2 spectral band was discovered by VIMS on the Saturn's satellites Dione, Hyperion, Iapetus and Phoebe [1]. The band position on the three first satellites corresponds to CO2 trapped in a complex material, but no indication exists whether this latter is water ice or some mineral or complex organic compound [1]. On Phoebe, the CO2 spectral band is consistent with solid CO2 or CO2 molecules trapped in the small cages of a clathrate hydrate structure [2]. It is thought that clathrate hydrates could play a significant role in the chemistry of the solar nebula [3] and in the physical evolution of astrophysical objects [4]. But so far, no clathrate hydrate structure has been observed in astrophysical environments. Moreover, identification of molecules trapped in a clathrate hydrate structure is extremely difficult because of the strong IR vibration modes of the water ice matrix. In this work, experimental IR reflectance spectra for CO2 clathrate hydrates are studied on grains and films. Clathrates are synthesized in a high pressure autoclave at low temperatures. IR spectral analysis is made with a low pressure and low temperature cryostat. These experimental conditions - 80 < T < 110 K, P~10-5 bar - are relevant to icy moons' surfaces. We have observed that the IR reflectance, in the spectral region (3 - 5 μm) characterized by H2O and CO2 high absorption coefficients, is strongly dependent on physical (size, surface) and optical (n and k) properties of the samples. The impact of these parameters on the CO2 clathrate IR reflectance spectrum will be presented. A comparison between the absorption bands of CO2 clathrate hydrates obtained in our lab and CO2 absorption bands as detected by VIMS on the icy satellites of Saturn will be shown. This experimental work confirms that VIMS data are not consistent with the presence of structure I CO2 clathrate hydrates on the surface of the icy moons. Possibility of having metastable structure II still remains unsolved and will be

  20. Nocturnal Measurements of HONO by Differential Optical Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wojtal, P.; McLaren, R.

    2011-12-01

    Differential optical absorption spectroscopy (DOAS) was used to quantify the concentration of HONO, NO2 and SO2 in the nocturnal urban atmosphere at York University over a period of one year. These measurements form a comprehensive HONO data set, including a large range of temperatures, relative humidity, surface conditions (snow, water, dry, etc.) and NO2 concentrations. Laboratory studies and observations within the nocturnal boundary layer reported in the literature suggest heterogeneous conversion of NO2 on surface adsorbed water as the major nighttime source of HONO. HONO formation and photolysis is believed to represent a major source term in the hydroxyl radical budget in polluted continental regions. Currently, most air quality models tend to significantly underpredict HONO, caused by the lack of understanding of HONO formation processes and the parameters that affect its concentration. Recently, we reported nocturnal pseudo steady states (PSS) of HONO in an aqueous marine environment and a conceptual model for HONO formation on aqueous surfaces was proposed. The data set collected at York University is being analyzed with a view towards further understanding the nighttime HONO formation mechanism and testing several hypotheses: 1) A HONO PSS can exist during certain times at night in an urban area in which the HONO concentration is independent of NO2, given the surface contains sufficient water coverage and is saturated with nitrogen containing precursors; 2) The concentration of HONO is positively correlated with temperature during periods where a PSS exists; 3) Different conversion efficiencies of NO2 to HONO exist on dry, wet and snow surfaces; 4) HONO formation has a NO2 order dependence between 0 and 2nd order, dependant on NO2 concentration, relative humidity, etc. The data set will be presented along with statistical analysis that sheds new light on the source of HONO in urban areas at night.

  1. 193Ir Mössbauer spectroscopy of Pt-IrO 2 nanoparticle catalysts developed for detection and removal of carbon monoxide from air

    NASA Astrophysics Data System (ADS)

    Sawicki, J. A.; Marcinkowska, K.; Wagner, F. E.

    2010-08-01

    Mössbauer spectroscopy of 73.0 keV gamma-ray transition in 193Ir and supplementary analytical techniques were used to study the microstructure and chemical form of polymer-supported hydrophobic bimetallic Pt-Ir catalysts for detection and removal of CO from humid air at ambient conditions. The catalysts, typically with a composition of 9 wt.% Pt and 1 wt.% Ir, were prepared by incipient wetness impregnation of polystyrene-divinylbenzene (SDB) granules with ethanol solutions of hexachloroplatinic and hexachloroiridic acids. This procedure, followed by reduction in H 2 or CO at only 200 °C or 250 °C, resulted in formation of highly-dispersed Pt-Ir particles usually smaller than 20 nm and having high catalytic activity and selectivity. Mössbauer spectra of 73.0 keV gamma-ray transition in 193Ir were taken after consecutive steps of preparation and exposure of catalysts to better understand and further improve the fabrication processes. In the as-impregnated state, iridium was found mostly as Ir(III) in [IrCl 6] 3- ions, with only a small fraction of Ir(IV) in [IrCl 6] 2- ions. The iridium in bimetallic clusters formed by reduction in hydrogen showed a strong tendency towards oxidation on exposure to air at room temperature, while Pt remained mostly metallic. In the most active and stable catalysts, the Ir and Pt in metallic regions of the clusters did not tend to segregate, unlike in Pt-Ir/silica-supported catalysts studied by us earlier. Further, this study shows that the IrO 2-like regions in the clusters exhibit stronger deviations from local symmetry and stoichiometry of crystalline IrO 2 than observed previously in Pt-Ir/silica catalysts. Our study also indicates that in the examined Pt-IrO 2 nanoparticles iridium largely provides the dissociative O 2 adsorption sites, while the CO adsorption occurs primarily at metallic Pt sites.

  2. Linear dichroism amplification: Adapting a long-known technique for ultrasensitive femtosecond IR spectroscopy

    SciTech Connect

    Rehault, Julien; Helbing, Jan; Zanirato, Vinicio; Olivucci, Massimo

    2011-03-28

    We demonstrate strong amplification of polarization-sensitive transient IR signals using a pseudo-null crossed polarizer technique first proposed by Keston and Lospalluto [Fed. Proc. 10, 207 (1951)] and applied for nanosecond flash photolysis in the visible by Che et al. [Chem. Phys. Lett. 224, 145 (1994)]. We adapted the technique to ultrafast pulsed laser spectroscopy in the infrared using photoelastic modulators, which allow us to measure amplified linear dichroism at kilohertz repetition rates. The method was applied to a photoswitch of the N-alkylated Schiff base family in order to demonstrate its potential of strongly enhancing sensitivity and signal to noise in ultrafast transient IR experiments, to simplify spectra and to determine intramolecular transition dipole orientations.

  3. Thermal properties of tannin extracted from Anacardium occidentale L. using TGA and FT-IR spectroscopy.

    PubMed

    Viswanath, Vinod; Leo, Vincent Vineeth; Prabha, S Sabna; Prabhakumari, C; Potty, V P; Jisha, M S

    2016-01-01

    The chemical nature of the polyphenols of cashew kernel testa has been determined. Testa contains tannins, which present large molecular complexity and has an ancient use as tanning agents. The use of tannins extracted from cashew testa, considered in many places as a waste, grants an extra value to the cashew. In this work we have analysed through high performance liquid chromatography, infrared spectroscopy (FT-IR) and thermo gravimetric analysis the average molecular weight, main functional groups and thermal properties of tannins extracted from Anacardium occidentale L. The results of these analyses are compared with the commercial grade tannic acid. The FT-IR spectra showed bands characteristic of C = C, C-C and OH bonds. This important bioactive compound present in the cashew nut kernel testa was suggested as an interesting economical source of antioxidants for use in the food and nutraceutical industry. PMID:26119693

  4. Linear dichroism amplification: Adapting a long-known technique for ultrasensitive femtosecond IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Réhault, Julien; Zanirato, Vinicio; Olivucci, Massimo; Helbing, Jan

    2011-03-01

    We demonstrate strong amplification of polarization-sensitive transient IR signals using a pseudo-null crossed polarizer technique first proposed by Keston and Lospalluto [Fed. Proc. 10, 207 (1951)] and applied for nanosecond flash photolysis in the visible by Che et al. [Chem. Phys. Lett. 224, 145 (1994)]. We adapted the technique to ultrafast pulsed laser spectroscopy in the infrared using photoelastic modulators, which allow us to measure amplified linear dichroism at kilohertz repetition rates. The method was applied to a photoswitch of the N-alkylated Schiff base family in order to demonstrate its potential of strongly enhancing sensitivity and signal to noise in ultrafast transient IR experiments, to simplify spectra and to determine intramolecular transition dipole orientations.

  5. Distributed nerve gases sensor based on IR absorption in hollow optical fiber

    NASA Astrophysics Data System (ADS)

    Viola, R.; Liberatore, N.; Luciani, D.; Mengali, S.; Pierno, L.

    2010-10-01

    The Nerve gases are persistent gases that appear as very challenging menace in homeland security scenarios, due to the low pressure vapor at ambient temperature, and the very low lethal concentrations. A novel approach to the detection and identification of these very hazardous volatile compounds in large areas such as airports, underground stations, big events arenas, aimed to a high selectivity (Low false alarm probability), has been explored under the SENSEFIB Corporate Project of Finmeccanica S.p.A. The technical demonstrator under development within the Project is presented. It is based on distributed line sensors performing infrared absorption measurements to reveal even trace amounts of target compounds from the retrieval of their spectral fingerprint. The line sensor is essentially constituted by a widely tunable external cavity quantum cascade laser (EC-QCL), coupled to IR thermoelectrically cooled MCT fast detectors by means of a infrared hollow core fibers (HCF). The air is sampled through several micro-holes along the HCF, by means of a micropump, while the infrared radiation travels inside the fiber from the source to the detector, that are optically coupled with the opposite apertures of the HCF. The architecture of the sensor and its principle of operation, in order to cover large areas with a few line sensors instead of with a grid of many point sensors, are illustrated. The sensor is designed to use the HCF as an absorption cell, exploiting long path length and very small volume, (e.g fast response), at the same time. Furthermore the distributed sensor allows to cover large areas and/or not easily accessible locations, like air ducts, with a single line sensor by extending the HCF for several tens of meters. The main components implemented in the sensor are described, in particular: the EC-QCL source to span the spectral range of wavelength between 9.15um and 9.85um; and the hollow core fiber, exhibiting a suitably low optical loss in this spectral

  6. Vibrational structure of C 84 and Sc 2@C 84 analyzed by IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hulman, M.; Pichler, T.; Kuzmany, H.; Zerbetto, F.; Yamamoto, E.; Shinohara, H. N.

    1997-06-01

    The isomer III of Sc 2@C 84 was separated by multi-cycle HPLC purification. We present temperature dependent IR absorption measurements of Sc 2@C 84 which have been performed between 50 and 300 K and between 400 and 5000 cm -1, respectively. The vibrational structure of the endohedral compound is compared to the structure of unfilled C 84. We find a strong overall broadening of the vibrational modes in Sc 2@C 84. Also some of the vibrational absorption lines are strongly enhanced if compared to the spectrum for the empty cage. With decreasing temperature, a dramatic narrowing of the lines in the spectral range between 700 and 800 cm -1 is observed.

  7. Noninvasive express diagnostics of pulmonary diseases based on control of patient's gas emission using methods of IR and terahertz laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Starikova, M. K.; Bulanova, A. A.; Bukreeva, E. B.; Karapuzikov, A. A.; Karapuzikov, A. I.; Kistenev, Y. V.; Klementyev, V. M.; Kolker, D. B.; Kuzmin, D. A.; Nikiforova, O. Y.; Ponomarev, Yu. N.; Sherstov, I. V.; Boyko, A. A.

    2013-11-01

    Pulmonary diseases diagnostics always occupies one of the key positions in medicine practices. A large variety of high technology methods are used today, but none of them cannot be used for early screening of pulmonary diseases. We discuss abilities of methods of IR and terahertz laser spectroscopy for noninvasive express diagnostics of pulmonary diseases on a base of analysis of absorption spectra of patient's gas emission, in particular, exhaled air. Experience in the field of approaches to experimental data analysis and hard-ware realization of gas analyzers for medical applications is also discussed.

  8. Residue-Specific Structural Kinetics of Proteins through the Union of Isotope Labeling, Mid-IR Pulse Shaping, and Coherent 2D IR Spectroscopy

    PubMed Central

    Middleton, Chris T.; Woys, Ann Marie; Mukherjee, Sudipta S.; Zanni, Martin T.

    2010-01-01

    We describe a methodology for studying protein kinetics using a rapid-scan technology for collecting 2D IR spectra. In conjunction with isotope labeling, 2D IR spectroscopy is able to probe the secondary structure and environment of individual residues in polypeptides and proteins. It is particularly useful for membrane and aggregate proteins. Our rapid-scan technology relies on a mid-IR pulse shaper that computer generates the pulse shapes, much like in an NMR spectrometer. With this device, data collection is faster, easier, and more accurate. We describe our 2D IR spectrometer, as well as protocols for 13C=18O isotope labeling, and then illustrate the technique with an application to the aggregation of the human islet amyloid polypeptide form type 2 diabetes. PMID:20472067

  9. [Evaluation of Malassezia species by Fourier transform infrared (FT-IR) spectroscopy].

    PubMed

    Ergin, Cağrı; Vuran, M Emre; Gök, Yaşar; Ozdemir, Durmuş; Karaarslan, Aydın; Kaleli, Ilknur; Zorbozan, Orçun; Kabay, Nilgün; Con, Ahmet Hilmi

    2011-10-01

    Malassezia species which are lipophilic exobasidiomycetes fungi, have been accepted as members of normal cutaneous flora as well as causative agent of certain skin diseases. In routine microbiology laboratory, species identification based on phenotypic characters may not yield identical results with taxonomic studies. Lipophilic and lipid-dependent Malassezia yeasts require lipid-enriched complex media. For this reason, Fourier transform infrared (FT-IR) spectroscopy analysis focused on lipid window may be useful for identification of Malassezia species. In this study, 10 different standard Malassezia species (M.dermatis CBS 9145, M.furfur CBS 7019, M.japonica CBS 9432, M.globosa CBS 7966, M.nana CBS 9561, M.obtusa CBS 7876, M.pachydermatis CBS 1879, M.slooffiae CBS 7956, M.sympodialis CBS 7222 and M.yamatoensis CBS 9725) which are human pathogens, have been analyzed by FT-IR spectroscopy following standard cultivation onto modified Dixon agar medium. Results showed that two main groups (M1; M.globosa, M.obtusa, M.sympodialis, M.dermatis, M.pachydermatis vs, M2; M.furfur, M.japonica, M.nana, M.slooffiae, M.yamatoensis) were discriminated by whole spectra analysis. M.obtusa in M1 by 1686-1606 cm-1 wavenumber ranges and M.japonicum in M2 by 2993-2812 cm-1 wavenumber ranges were identified with low level discrimination power. Discriminatory areas for species differentiation of M1 members as M.sympodialis, M.globosa and M.pachydermatis and M2 members as M.furfur and M.yamatoensis could not be identified. Several spectral windows analysis results revealed that FT-IR spectroscopy was not sufficient for species identification of culture grown Malassezia species. PMID:22090301

  10. Water of Hydration Dynamics in Minerals Gypsum and Bassanite: Ultrafast 2D IR Spectroscopy of Rocks.

    PubMed

    Yan, Chang; Nishida, Jun; Yuan, Rongfeng; Fayer, Michael D

    2016-08-01

    Water of hydration plays an important role in minerals, determining their crystal structures and physical properties. Here ultrafast nonlinear infrared (IR) techniques, two-dimensional infrared (2D IR) and polarization selective pump-probe (PSPP) spectroscopies, were used to measure the dynamics and disorder of water of hydration in two minerals, gypsum (CaSO4·2H2O) and bassanite (CaSO4·0.5H2O). 2D IR spectra revealed that water arrangement in freshly precipitated gypsum contained a small amount of inhomogeneity. Following annealing at 348 K, water molecules became highly ordered; the 2D IR spectrum became homogeneously broadened (motional narrowed). PSPP measurements observed only inertial orientational relaxation. In contrast, water in bassanite's tubular channels is dynamically disordered. 2D IR spectra showed a significant amount of inhomogeneous broadening caused by a range of water configurations. At 298 K, water dynamics cause spectral diffusion that sampled a portion of the inhomogeneous line width on the time scale of ∼30 ps, while the rest of inhomogeneity is static on the time scale of the measurements. At higher temperature, the dynamics become faster. Spectral diffusion accelerates, and a portion of the lower temperature spectral diffusion became motionally narrowed. At sufficiently high temperature, all of the dynamics that produced spectral diffusion at lower temperatures became motionally narrowed, and only homogeneous broadening and static inhomogeneity were observed. Water angular motions in bassanite exhibit temperature-dependent diffusive orientational relaxation in a restricted cone of angles. The experiments were made possible by eliminating the vast amount of scattered light produced by the granulated powder samples using phase cycling methods. PMID:27385320

  11. FT-IR and FT-NIR Raman spectroscopy in biomedical research

    NASA Astrophysics Data System (ADS)

    Naumann, D.

    1998-06-01

    FT-IR and FT-NIR Raman spectra of intact microbial, plant animal or human cells, tissues, and body fluids are highly specific, fingerprint-like signatures which can be used to discriminate between diverse microbial species and strains, characterize growth-dependent phenomena and cell-drug interactions, and differentiate between various disease states. The spectral information potentially useful for biomedical characterizations may be distributed over the entire infrared region of the electromagnetic spectrum, i.e. over the near-, mid-, and far-infrared. It is therefore a key problem how the characteristic vibrational spectroscopic information can be systematically extracted from the infrared spectra of complex biological samples. In this report these questions are addressed by applying factor and cluster analysis treating the classification problem of microbial infrared spectra as a model task. Particularly interesting applications arise by means of a light microscope coupled to the FT-IR spectrometer. FT-IR spectra of single microcolonies of less than 40 μm in diameter can be obtained from colony replica applying a stamping technique that transfers the different, spatially separated microcolonies from the culture plate to a special IR-sample holder. Using a computer controlled x,y-stage together with mapping and video techniques, the fundamental tasks of microbiological analysis, namely detection, enumeration, and differentiation of micro-organisms can be integrated in one single apparatus. Since high quality, essentially fluorescence free Raman spectra may now be obtained in relatively short time intervals on previously intractable biological specimens, FT-IR and NIR-FT-Raman spectroscopy can be used in tandem to characterize biological samples. This approach seems to open up new horizons for biomedical characterizations of complex biological systems.

  12. Characterization of laser-treated Opuntia using FT-IR spectroscopy and thermal analysis

    NASA Astrophysics Data System (ADS)

    Mejías Díaz, K. D.; Flores Reyes, T.; Ponce Cabrera, L.; Domínguez Sánchez, M.; Arronte García, M.; de Posada Piñán, E.

    2013-07-01

    This paper presents the characterization of Opuntia samples whose thorns were removed by laser pulses. The characterization was performed by Fourier transform infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC). In this study we performed a comparative analysis of samples before and after treatment by using a Nd:YAG laser emitting at 1064 nm with an energy variable of up to 0.9 J. It was determined that no significant morphological or compositional changes had taken place in the cactus epidermis due to the laser treatment.

  13. Structure-Activity Relations In Enzymes: An Application Of IR-ATR Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Fringeli, Urs P.; Ahlstrom, Peter; Vincenz, Claudius; Fringeli, Marianna

    1985-12-01

    Relations between structure and specific activity in immobilized acetylcholinesterase (ACNE) have been studied by means of pH- and Ca++-modulation technique combined with attenuated total reflection (ATR) infrared (IR) spectroscopy and enzyme activity measurement. Periodic modulation of pH and Ca++-concentration enabled a periodic on-off switching of about 40% of the total enzyme activity. It was found that about 0.5 to 1% of the amino acids were involved in this process. These 15 to 30 amino acids assumed antiparallel pleated sheet structure in the inhibited state and random and/or helical structure in the activated state.

  14. Synthesis and investigation of iron (II) dioximates with arsine derivatives by Moessbauer and IR spectroscopy

    SciTech Connect

    Zubareva, V.E.; Turte, K.I.; Shafranskii, V.N.; Bulgak, I.I.; Batyr, D.G.; Stukan, R.A.

    1988-06-01

    New compounds with the formula (Fe/sup II/(dioximate)/sub 2/L/sub 2/), where dioximate stands for monodeprotonated anions of dimethylglyoxime (dmgH), diphenylglyoxime (dfgH), 1,2-cyclohexanedione dioxime (nioxH), and ..cap alpha..-furildioxime (furgH), and L stands for di-n-butylphenylarsine (AsBut/sub 2/Ph) and triethylarsine (AsEt/sub 3/), have been investigated by Moessbauer and IR spectroscopy. The Moessbauer spectra of the compounds indicated at 80 and 300/sup 0/K consist of doublets, whose parameters correspond to the low-spin state of iron (II).

  15. Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

    NASA Technical Reports Server (NTRS)

    Fan, Wendy

    2011-01-01

    The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

  16. Analysis of pathological and non-pathological human skeletal remains by FT-IR spectroscopy.

    PubMed

    Nagy, Gergely; Lorand, Tamas; Patonai, Zoltan; Montsko, Gergely; Bajnoczky, Istvan; Marcsik, Antonia; Mark, Laszlo

    2008-02-25

    In this study, we report the chemical analyses of various non-pathological, tuberculosis and syphilis infected bone samples from different burial environments by Fourier transform infrared spectroscopy (FT-IR), in the framework of a general study of diagenesis. Dating human skeletal remains is one of the most important and yet unreliable aspects of forensic anthropology. In this paper, a new method has been suggested, using the crystallinity index and carbonate-phosphate index as a means of distinction between recent and archaeological, anthropological bone samples. Pathological bone samples were analyzed with the same method to see if changes in crystallinity interfere with the process of dating. PMID:17574360

  17. Determination of molecular line parameters for acrolein (C 3H 4O) using infrared tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Harward, Charles N.; Thweatt, W. David; Baren, Randall E.; Parrish, Milton E.

    2006-04-01

    Acrolein (C 3H 4O) molecular line parameters, including infrared (IR) absorption positions, strengths, and nitrogen broadened half-widths, must be determined since they are not included in the high resolution transmission (HITRAN) molecular absorption database of spectral lines. These parameters are required for developing a quantitative analytical method for measuring acrolein in a single puff of cigarette smoke using tunable diode laser absorption spectroscopy (TDLAS). The task is complex since acrolein has many highly overlapping infrared absorption lines in the room temperature spectrum and the cigarette smoke matrix contains thousands of compounds. This work describes the procedure for estimating the molecular line parameters for these overlapping absorption lines in the wavenumber range (958.7-958.9 cm -1) using quantitative reference spectra taken with the infrared lead-salt TDLAS instrument at different pressures and concentrations. The nitrogen broadened half-width for acrolein is 0.0937 cm -1 atm -1 and to our knowledge, is the first time it has been reported in the literature.

  18. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1975-01-01

    Data were obtained which will provide a test of the accuracy of the differential absorption method for trace contaminant detection in many-component gas mixtures. The necessary accurate absorption coefficient determinations were carried out for several gases; acetonitrile, 1,2-dichloroethane, Freon-113, furan, methyl ethyl ketone, and t-butyl alcohol. The absorption coefficients are displayed graphically. An opto-acoustic method was tested for measuring absorbance, similar to the system described by Dewey.

  19. Fourier Transform Infrared (FT-IR) Spectroscopy of Atmospheric Trace Gases HCl, NO and SO2

    NASA Technical Reports Server (NTRS)

    Haridass, C.; Aw-Musse, A.; Dowdye, E.; Bandyopadhyay, C.; Misra, P.; Okabe, H.

    1998-01-01

    Fourier Transform Infrared (FT-IR) spectral data have been recorded in the spectral region 400-4000/cm of hydrogen chloride and sulfur dioxide with I/cm resolution and of nitric oxide with 0.25 cm-i resolution, under quasi-static conditions, when the sample gas was passed through tubings of aluminum, copper, stainless steel and teflon. The absorbance was measured for the rotational lines of the fundamental bands of (1)H(35)Cl and (1)H(37)Cl for pressures in the range 100-1000 Torr and for the (14)N(16)O molecule in the range 100-300 Torr. The absorbance was also measured for individual rotational lines corresponding to the three modes of vibrations (upsilon(sub 1) - symmetric stretch, upsilon(sub 2) - symmetric bend, upsilon(sub 3) - anti-symmetric stretch) of the SO2 molecule in the pressure range 25-150 Torr. A graph of absorbance versus pressure was plotted for the observed rotational transitions of the three atmospherically significant molecules, and it was found that the absorbance was linearly proportional to the pressure range chosen, thereby validating Beer's law. The absorption cross-sections were determined from the graphical slopes for each rotational transition recorded for the HCl, NO and SO2 species. Qualitative and quantitative spectral changes in the FT-IR data will be discussed to identify and characterize various tubing materials with respect to their absorption features.

  20. Interaction of mineral surfaces with simple organic molecules by diffuse reflectance IR spectroscopy (DRIFT)

    SciTech Connect

    Thomas, Joan E.; Kelley, Michael J.

    2008-06-01

    Diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS) was used to characterize multi-layers of lysine, glutamic acid and salicylic acid on -alumina and kaolinite surfaces. The results agreed well with those previously obtained by ATR-IR in aqueous media where available, indicating that DRIFT may be regarded as effectively an in-situ spectroscopy for these materials. In the case of salicylic acid adsorption onto γ-alumina, DRIFTS was used to identify monolayer coverage and to detect molecules down to coverage of 3% of a monolayer. The spectroscopic results as to coverage were confirmed by analysis of the solutions used for treatment. The spectra obtained allowed identification of changes in the bonding environment with increasing surface coverage. DRIFTS, offers several advantages in terms of materials, experimental technique and data treatment, motivating further investigations.

  1. Mineral Specific IR Molar Absorption Coefficients for Routine Water Determination in Olivine, SiO2 polymorphs and Garnet

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Koch-Mueller, M.; Reichart, P.; Rhede, D.; Thomas, R.

    2007-12-01

    Conventionally applied Infrared (IR) calibrations [1, 2] for quantitative water analyses in solids are established on hydrous minerals and glasses with several wt% water. These calibrations are based on a negative correlation between the IR molar absorption coefficient (ɛ) for water and the mean wavenumber of the corresponding OH pattern. The correlation reflects the dependence of the OH band position on the appropriate O- H...O distances and thereby the magnitude of the dipole momentum which is proportional to the band intensity. However, it has been observed that these calibrations can not be adopted to nominally anhydrous minerals (NAMs) [3].To study the potential dependence of ɛ on structure and chemistry in NAMs we synthesized olivine and SiO2 polymorphs with specific isolated hydroxyl point defects, e.g. quartz, coesite and stishovite with B3++H+=Si4+ and/or Al3++H+=Si4+ substitutions. Experiments were performed with water in excess in piston cylinder and multi-anvil presses. Single crystal IR spectra demonstrate that we successfully managed to seperate generally complex OH patterns as e.g. observed in natural quartz and synthetic coesite. We quantified sample water contents of both natural samples and our run products by applying proton-proton-scattering [4], confocal microRaman spectroscopy [5] and Secondary Ion mass spectrometry. Resulting water concentrations were used to calculate new mineral specific ɛs. For olivine with the mean wavenumber of 3517 cm-1 we determined an ɛ value of 41,000±5,000 lmol-1H2Ocm-2. Quantification of olivine with the mean wavenumber of 3550 cm-1 in contrast resulted in an ɛ value of 47,000±1,000 lmol-1H2Ocm-2. Taking into account previous studies [6, 7] there is evidence to suggest a linear wavenumber dependent correlation for olivine, where ɛ increases with decreasing wavenumber. In case of the SiO2 system it turns out that the magnitude of ɛ within one structure type is independent of the liable OH point defect and

  2. Spectroscopy and electronic structure of Sr2YRuO6 and Sr2YRu0.75Ir0.25O6

    NASA Astrophysics Data System (ADS)

    Guedes, E. B.; Abbate, M.; Abud, F.; Jardim, R. F.; Vicentin, F. C.; Mossanek, R. J. O.

    2016-07-01

    We study the electronic structure of the Sr2YRuO6 and Sr2YRu0.75Ir0.25O6 compounds using x-ray (resonant) photoemission and absorption spectroscopies. The experimental results are interpreted with first-principles calculations, which give a good agreement with all the spectra. These results show that, although the spin-orbit coupling does not induce orbital anisotropies in these systems, it is responsible for the reduction of magnetic moments within the the Ir5 +O6 octahedra, weakening the magnetic ordering in the substituted system. Finally, our findings support the idea that the canting of Ru5 + magnetic moments actually plays an important role in the stabilization of the intriguing magnetic ordering in the Sr2YRuO6 compound.

  3. Aerosol particle absorption spectroscopy by photothermal modulation of Mie scattered light

    SciTech Connect

    Campillo, A.J.; Dodge, C.J.; Lin, H.B.

    1981-09-15

    Absorption spectroscopy of suspended submicron-sized aqueous ammonium-sulfate aerosol droplets has been performed by employing a CO/sub 2/ laser to photothermally modulate visible Mie scattered light. (AIP)

  4. Transient absorption spectroscopy using the super-ACO storage ring FEL

    NASA Astrophysics Data System (ADS)

    Renault, Eric; Nahon, Laurent; Nutarelli, Daniele; Garzella, David; Merola, F.; Couprie, Marie-Emmanuelle

    2000-04-01

    The Super-ACO storage ring FEL is operating with a high average power in the UV range (300 mW at 350 nm), and recently at wavelengths down to 300 nm. In addition this source exhibits high stability and long lifetime which makes it a unique tool for user applications. The coupling of the FEL with other synchrotron based sources (bending magnet and undulator) opens many unexplored possibilities for various types of two-color time-resolved spectroscopies. Presently, we are developing a two-color experiment where we study the sub-nanosecond time-resolved absorption of different chromophoric compounds. In this type of pump-probe experiments, the intense UV pulse of the Super-ACO FEL is used to prepare a high initial concentration of chromophores in their first singlet electronic excited state. The nearby bending magnet synchrotron radiation provides on the other hand a pulsed, white light continuum ranging from UV to IR, which is naturally synchronized with the FEL pulses and can be used to probe the photochemical subsequent events and the transient species. With a dye molecule (POPOP), we have obtained a two-color effect which demonstrates the feasibility of the experiment in terms of flux. Applications on various chromophores of biological interest are planned.

  5. Nitric oxide breath testing by tunable-diode laser absorption spectroscopy: application in monitoring respiratory inflammation

    NASA Astrophysics Data System (ADS)

    Roller, Chad; Namjou, Khosrow; Jeffers, James D.; Camp, Mark; Mock, Adam; McCann, Patrick J.; Grego, Joe

    2002-10-01

    We used a high-resolution mid-IR tunable-laser absorption spectroscopy (TLAS) system with a single IV-VI laser operating near 5.2 mum to measure the level of exhaled nitric oxide (eNO) in human breath. A method of internal calibration using simultaneous eNO and exhaled CO2 measurements eliminated the need for system calibration with gas standards. The results observed from internally calibrating the instrument for eNO measurements were compared with measurements of eNO calibrated to gas standards and were found to be similar. Various parameters of the TLAS system for eNO breath testing were examined and include gas cell pressure, exhalation time, and ambient NO concentrations. A reduction in eNO from elevated concentrations (approx44 parts in 109) to near-normal levels (<20 parts in 109) from an asthmatic patient was observed after the patient had received treatment with an inhaled glucocorticoid anti-inflammatory medication. Such measurements can help in evaluating airway inflammation and in monitoring the effectiveness of anti-inflammatory therapies.

  6. Probing Intermolecular Interactions in Polycyclic Aromatic Hydrocarbons with 2D IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Krummel, Amber

    2014-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and impact geochemical processes that are critical to sustainable energy resources. For example, asphaltenes exist naturally in geologic formations and their aggregates heavily impact the petroleum economy. Unfortunately, the chemical dynamics that drive asphaltene nanoaggregation processes are still poorly understood. Solvent dynamics and intermolecular interactions such as π-stacking interactions play integral roles in asphaltene nanoaggregation. Linear and nonlinear vibrational spectroscopy including two-dimensional infrared spectroscopy (2DIR), are well suited to explore these fundamental interactions. Teasing apart the vibrational characteristics in PAHs that model asphaltenic compounds represents an important step towards utilizing 2D IR spectroscopy to understand the intermolecular interactions that are prevalent in asphaltene nanoaggregation. A solar dye, N,N'-Dioctyl-3,4,9,10-perylenedicarboximide, is used in this work to model aphaltenes. Carbonyl and ring vibrations are used to probe the nanoaggregates of the model compounds. However, the characteristics of these normal modes change as a function of the size of the conjugated ring system. Thus, in order to fully understand the nature of these normal modes, we include a systematic study of a series of quinones. Our investigation employs a combination of 2DIR spectroscopy and electronic structure calculations to explore vibrational coupling in quinones and PAHs. We compare the calculated vibrational characteristics to those extracted from 2DIR spectra. ATK acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  7. Determination of leachate compounds relevant for landfill aftercare using FT-IR spectroscopy.

    PubMed

    Lenz, Sabine; Böhm, Katharina; Ottner, Reinhold; Huber-Humer, Marion

    2016-09-01

    Controlling and monitoring of emissions from municipal solid waste (MSW) landfills is important to reduce environmental damage and health risks. Therefore, simple and meaningful monitoring tools are required. This paper presents how Fourier Transform Infrared (FT-IR) Spectroscopy can be used to monitor leachate from various landfill sites. The composition of percolated leachate provides information about reactivity or stability of organic matter in landfills. Chemical compounds of investigated leachate are depicted by distinct spectral pattern. Partial least squares regression (PLS-R) models, a multivariate analysis tool, were developed based on infrared spectra to determine simultaneously conventional parameters such as ammonium, nitrate, sulfate, and dissolved organic carbon. The developed models are appropriate for application in waste management practice with respect to their excellent coefficients of determination, namely R(2)=0.99, 0.99, 0.98, and 0.98, their low errors of cross-validation and their high ratios of performance to deviation (RPD=9.3, 12.5, 6.5, 7.3). Thus, FT-IR spectroscopy turned out to be a reliable, time-saving tool to determine four parameters relevant for landfill aftercare monitoring by one single easy adaptable measurement. PMID:26951718

  8. New ultrarapid-scanning interferometer for FT-IR spectroscopy with microsecond time-resolution.

    PubMed

    Süss, B; Ringleb, F; Heberle, J

    2016-06-01

    A novel Fourier-transform infrared (FT-IR) rapid-scan spectrometer has been developed (patent pending EP14194520.4) which yields 1000 times higher time resolution as compared to conventional rapid-scanning spectrometers. The central element to achieve faster scanning rates is based on a sonotrode whose front face represents the movable mirror of the interferometer. A prototype spectrometer with a time resolution of 13 μs was realized, capable of fully automated long-term measurements with a flow cell for liquid samples, here a photosynthetic membrane protein in solution. The performance of this novel spectrometer is demonstrated by recording the photoreaction of bacteriorhodopsin initiated by a short laser pulse that is synchronized to the data recording. The resulting data are critically compared to those obtained by step-scan spectroscopy and demonstrate the relevance of performing experiments on proteins in solution. The spectrometer allows for future investigations of fast, non-repetitive processes, whose investigation is challenging to step-scan FT-IR spectroscopy. PMID:27370432

  9. Cyclohexene Photo-oxidation over Vanadia Catalyst Analyzed by Time Resolved ATR-FT-IR Spectroscopy

    SciTech Connect

    Frei, Heinz; Mul, Guido; Wasylenko, Walter; Hamdy, M. Sameh; Frei, Heinz

    2008-06-04

    Vanadia was incorporated in the 3-dimensional mesoporous material TUD-1 with a loading of 2percent w/w vanadia. The performance in the selective photo-oxidation of liquid cyclohexene was investigated using ATR-FT-IR spectroscopy. Under continuous illumination at 458 nm a significant amount of product, i.e. cyclohexenone, was identified. This demonstrates for the first time that hydroxylated vanadia centers in mesoporous materials can be activated by visible light to induce oxidation reactions. Using the rapid scan method, a strong perturbation of the vanadyl environment could be observed in the selective oxidation process induced by a 458 nm laser pulse of 480 ms duration. This is proposed to be caused by interaction of the catalytic centre with a cyclohexenyl hydroperoxide intermediate. The restoration of the vanadyl environment could be kinetically correlated to the rate of formation of cyclohexenone, and is explained by molecular rearrangement and dissociation of the peroxide to ketone and water. The ketone diffuses away from the active center and ATR infrared probing zone, resulting in a decreasing ketone signal on the tens of seconds time scale after initiation of the photoreaction. This study demonstrates the high potential of time resolved ATR FT-IR spectroscopy for mechanistic studies of liquid phase reactions by monitoring not only intermediates and products, but by correlating the temporal behavior of these species to molecular changes of the vanadyl catalytic site.

  10. New ultrarapid-scanning interferometer for FT-IR spectroscopy with microsecond time-resolution

    NASA Astrophysics Data System (ADS)

    Süss, B.; Ringleb, F.; Heberle, J.

    2016-06-01

    A novel Fourier-transform infrared (FT-IR) rapid-scan spectrometer has been developed (patent pending EP14194520.4) which yields 1000 times higher time resolution as compared to conventional rapid-scanning spectrometers. The central element to achieve faster scanning rates is based on a sonotrode whose front face represents the movable mirror of the interferometer. A prototype spectrometer with a time resolution of 13 μs was realized, capable of fully automated long-term measurements with a flow cell for liquid samples, here a photosynthetic membrane protein in solution. The performance of this novel spectrometer is demonstrated by recording the photoreaction of bacteriorhodopsin initiated by a short laser pulse that is synchronized to the data recording. The resulting data are critically compared to those obtained by step-scan spectroscopy and demonstrate the relevance of performing experiments on proteins in solution. The spectrometer allows for future investigations of fast, non-repetitive processes, whose investigation is challenging to step-scan FT-IR spectroscopy.

  11. Absorption spectroscopy in hollow-glass waveguides using infrared laser diodes

    SciTech Connect

    Blake, Thomas A.; Kelly, James F.; Stewart, Timothy L.; Hartman, John S.; Sharpe, Steven W.; Sams, Robert L.

    2002-07-10

    Hollow-glass waveguides may be a viable technology that, in some cases, may supplant heavier multi-pass cells such as White or Herriott cells for performing trace detection using tunable diode laser absorption spectroscopy. We report here a series of experiments for testing the suitability of waveguides for infrared spectroscopy. The loss characteristics of 1 mm bore diameter waveguides have been measured for straight and coiled lengths. Using direct absorption spectroscopy we have found that the absorption pathlength is approximately equal to the physical length of the waveguide. Broadband FM diode laser spectroscopy produces a comparable signal-to-noise ratio with less than a second of signal averaging. Finally, we have also performed near-infrared spectroscopy of nitrous oxide flowing through a waveguide using a telecommunications diode laser.

  12. Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test

    PubMed Central

    Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

    2015-01-01

    Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness. PMID:26889359

  13. Utility of FT-IR imaging spectroscopy in estimating differences between the quality of bovine blastocysts

    NASA Astrophysics Data System (ADS)

    Wiecheć, A.; Opiela, J.; Lipiec, E.; Kwiatek, W. M.

    2013-10-01

    This study was conducted to verify whether the FT-IR spectroscopy and Focal Plane Array (FPA) imaging can be successfully applied to estimate the quality of bovine blastocysts (on the basis of the concentration of nucleic acids and amides). The FT-IR spectra of inner cell mass from blastocysts of three different culture systems were examined. The spectral changes between blastocysts were analyzed in DNA (spectral range of 1240-950 cm-1) and protein amides (1800-1400 cm-1). Blastocyst 1 (BL1-HA) was developed from the fertilized oocyte cultured with low concentration of hialuronian (HA), Blastocyst 2 and 3 were developed from the oocytes cultured in standard conditions. Cleavage stage blastocyst 2 (BL2-SOF) has been cultured in SOF medium while blastocyst 3 (BL3-VERO) was cultured in co-culture with VERO cells. The multivariate statistical analysis (Hierarchical Cluster Analysis - HCA and Principal Component Analysis - PCA) of single cells spectra showed high similarity of cells forming the inner cell mass within single blastocyst. The main variance between the three examined blastocysts was related to amides bands. Differences in the intensities of the amides' peaks between the bovine blastocysts derived from different culture systems indicated that specific proteins reflecting the appearance of a new phenotype were produced. However, for the three blastocysts, the α-helix typical peak was twice more intensive than the β-sheet typical peak suggesting that the differentiation processes had been started. Taking into account the quantitative and qualitative composition of the protein into examined blastocysts, it can be assumed, that the quality of the BL1-HA turned out much more similar to BL3-VERO than to BL2-SOF. FT-IR spectroscopy can be successfully applied in reproductive biology research for quality estimation of oocytes and embryos at varied stages of their development. Moreover this technique proved to be particularly useful when the quantity of the

  14. Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test.

    PubMed

    Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

    2015-01-01

    Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness. PMID:26889359

  15. Far-Ir Action Spectroscopy of Aminophenol and Ethylvanillin: Experiment and Theory

    NASA Astrophysics Data System (ADS)

    Yatsyna, Vasyl; Feifel, Raimund; Zhaunerchyk, Vitali; Bakker, Daniël; Rijs, Anouk

    2015-06-01

    Investigations of molecular structure and conformational isomerism are at the forefront of today's biophysics and biochemistry. In particular, vibrations excited by far-IR radiation can be highly sensitive to the molecular 3D structure as they are delocalized over large parts of the molecule. Current theoretical predictions of vibrational frequencies in the far-IR range are not accurate enough because of the non-local character and anharmonicity of these vibrations. Therefore experimental studies in the far-IR are vital to guide theory towards improved methodology. In this work we present the conformer-specific far-IR spectra of aminophenol and ethylvanillin molecules in the range of 220-800 wn utilizing ion-dip action spectroscopy carried out at the free electron laser FELIX in Nijmegen, Netherlands. The systems studied are aromatic molecules with important functional groups such as the hydroxyl (OH) and amino (NH_2) groups in aminophenol, and the hydroxyl, ethoxy (OCH_2CH_3) and formyl (CHO) groups in ethylvanillin. The experimental spectra show well resolved conformer-specific vibrational bands. In the case of ethylvanillin only two planar conformers have been observed under supersonic jet expansion conditions. Despite the fact that these conformers differ only in the position of oxygen of the formyl group with respect to ethoxy group, they are well distinguishable in far-IR spectra. The capability of numerical methods based on density functional theory (DFT) for predicting vibrational frequencies in this spectral region within the harmonic approximation has been investigated by using several hybrid-functionals such as B3LYP, PBE0, B2PLYP and CAM-B3LYP. An anharmonic correction based on vibrational second order perturbation theory approach was also applied. We have found that the methods we considered are well suited for the assignment of far-IR vibrational features except the modes which are strongly anharmonic, like the NH_2 wagging mode in aminophenol which

  16. Direct and quantitative photothermal absorption spectroscopy of individual particulates

    SciTech Connect

    Tong, Jonathan K.; Hsu, Wei-Chun; Eon Han, Sang; Burg, Brian R.; Chen, Gang; Zheng, Ruiting; Shen, Sheng

    2013-12-23

    Photonic structures can exhibit significant absorption enhancement when an object's length scale is comparable to or smaller than the wavelength of light. This property has enabled photonic structures to be an integral component in many applications such as solar cells, light emitting diodes, and photothermal therapy. To characterize this enhancement at the single particulate level, conventional methods have consisted of indirect or qualitative approaches which are often limited to certain sample types. To overcome these limitations, we used a bilayer cantilever to directly and quantitatively measure the spectral absorption efficiency of a single silicon microwire in the visible wavelength range. We demonstrate an absorption enhancement on a per unit volume basis compared to a thin film, which shows good agreement with Mie theory calculations. This approach offers a quantitative approach for broadband absorption measurements on a wide range of photonic structures of different geometric and material compositions.

  17. Miniaturized King furnace permits absorption spectroscopy of small samples

    NASA Technical Reports Server (NTRS)

    Ercoli, B.; Tompkins, F. S.

    1968-01-01

    Miniature King-type furnace, consisting of an inductively heated, small diameter tantalum tube supported in a radiation shield eliminates the disadvantages of the conventional furnace in obtaining absorption spectra of metal vapors.

  18. The use of CNDO in spectroscopy. XV. Two photon absorption

    NASA Astrophysics Data System (ADS)

    Marchese, Francis T.; Seliskar, C. J.; Jaffé, H. H.

    1980-04-01

    Two-photon absorptivities have been calculated within the CNDO/S-CI molecular orbital framework of Del Bene and Jaffé utilizing the second order time dependent perturbation equations of Göppert-Mayer and polarization methods of McClain. Good agreement is found between this theory and experiment for transition energies, symmetries, and two-photon absorptivities for the following molecules: biphenyl, terphenyl, 2,2'-difluorobiphenyl, 2,2'-bipyridyl, phenanthrene, and the isoelectronic series: fluorene, carbazole, dibenzofuran.

  19. Experimental study of the light absorption in sea water by thermal lens spectroscopy

    NASA Astrophysics Data System (ADS)

    Velásquez, A.; Sira, E.; Silva, S.; Cabrera, H.

    2016-01-01

    Thermal lens spectroscopy is well known as highly sensitive technique enabling measurements of low absorption and concentration determination of various compounds. The optical absorption coefficients of doubly distilled water and samples of water from different places of the open Ocean and different coastal regions have been measured at 532.8 nm wavelength using this technique. The method enables sensitive, rapid and reproducible determination of small variations of the absorption coefficient which are related with small trace contaminations in sea water.

  20. Spectroscopy and nonlinear optical absorption of bis(diphenylamino) diphenyl polyenes

    NASA Astrophysics Data System (ADS)

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

    1999-10-01

    The spectroscopy and nonlinear absorption of bis(diphenylamino) diphenyl polyenes have been studied in octane and dichloromethane solvents. The amines exhibit high fluorescence quantum yield and two photon excited emission. Two photon absorption cross section, (sigma) 2, was measured by Z-scan experiments. Strong two photon absorption is indicated by high values for (sigma) 2. Solvent has strong influence in the measurement of (sigma) 2 values.

  1. Trace gas absorption spectroscopy using laser difference-frequency spectrometer for environmental application

    NASA Technical Reports Server (NTRS)

    Chen, W.; Cazier, F.; Boucher, D.; Tittel, F. K.; Davies, P. B.

    2001-01-01

    A widely tunable infrared spectrometer based on difference frequency generation (DFG) has been developed for organic trace gas detection by laser absorption spectroscopy. On-line measurements of concentration of various hydrocarbons, such as acetylene, benzene, and ethylene, were investigated using high-resolution DFG trace gas spectroscopy for highly sensitive detection.

  2. Generation and reactivity of the phenyl cation in cryogenic argon matrices: monitoring the reactions with nitrogen and carbon monoxide directly by IR spectroscopy.

    PubMed

    Winkler, Michael; Sander, Wolfram

    2006-08-18

    The phenyl cation 1 has been prepared by co-deposition of iodobenzene 6 or bromobenzene 7 with a microwave-induced argon plasma and characterized by IR spectroscopy in cryogenic argon matrices. The cation can clearly be identified by its strongest absorption at 3110 cm(-1) that is rapidly bleached upon visible light irradiation. This characteristic band is observed neither in the conventional photochemistry of 6 or 7 nor in discharge experiments with alkyl halides or chlorobenzene. The latter finding is in line with energetic considerations. According to density functional theory (DFT) computations, the strongest absorption of 1 is caused by a C-H stretching vibration that involves almost entirely the ortho-hydrogens. This is confirmed by isotopic labeling experiments. Co-deposition of halobenzene/N2 mixtures leads to a decrease of the 3110 cm(-1) absorption, whereas several new signals are detected in the 2200-2400 cm(-1) range of the IR spectrum. Annealing of a matrix that contains 1 and 1% N2 leads to an increase of a broad band at 2260 cm(-1) that is assigned to the benzenediazonium ion 2. A sharp signal at 2327 cm(-1) that had previously been assigned to the N-N stretching vibration of 2 is due to molecular nitrogen. The mechanism that triggers the IR activity of N2 is not yet understood. Annealing of a matrix that contains 1 and 0.5% CO leads to an increase of a broad band at 2217 cm(-1) that is considerably stronger than the 2260 cm(-1) absorption of 2. This signal is assigned to the C-O stretching vibration of the benzoyl cation 12, in excellent agreement with previous investigations of 12 in superacidic media. Some consequences of the measured frequencies with regard to bonding in 2 and 12 are discussed. PMID:16901116

  3. Protein Dynamics Studied with Ultrafast 2D IR Vibrational Echo Spectroscopy

    PubMed Central

    THIELGES, MEGAN C.; FAYER, MICHAEL D.

    2012-01-01

    CONSPECTUS Proteins, enzymes, and other biological molecules undergo structural dynamics as an intrinsic part of their biological functions. While many biological processes occur on the millisecond, second, and even longer time scales, the fundamental structural dynamics that eventually give rise to such processes occur on much faster time scales. Many decades ago, chemical kineticists focused on the inverse of the reaction rate constant as the important time scale for a chemical reaction. However, through transition state theory and a vast amount of experimental evidence, we now know that the key events in a chemical reaction can involve structural fluctuations that take a system of reactants to its transitions state, the crossing of a barrier, and the eventual relaxation to product states. Such dynamics occur on very fast time scales. Today researchers would like to investigate the fast structural fluctuations of biological molecules to gain an understanding of how biological processes proceed from simple structural changes in biomolecules to the final, complex biological function. The study of the fast structural dynamics of biological molecules requires experiments that operate on the appropriate time scales, and in this Account, we discuss the application of ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy to the study of dynamics. The 2D IR vibrational echo experiment is akin to 2D NMR, but it operates on time scales many orders of magnitude faster. In the experiments, a particular vibrational oscillator serves as a vibrational dynamics probe. As the structure of the protein evolves in time, the structural changes are manifested as time dependent changes in the frequency of the vibrational dynamics probe. The 2D IR vibrational echo experiments can track the vibrational frequency evolution, which we then relate to the time evolution of the protein structure. In particular, we measured protein substate interconversion for mutants of

  4. 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.

  5. Structure of saligenin: microwave, UV and IR spectroscopy studies in a supersonic jet combined with quantum chemistry calculations.

    PubMed

    Kumar, Sumit; Singh, Santosh K; Calabrese, Camilla; Maris, Assimo; Melandri, Sonia; Das, Aloke

    2014-08-28

    In this study, we have determined the structure of a medicinally important molecule saligenin (2-hydroxybenzyl alcohol) using UV, IR and microwave absorption spectroscopy in a supersonic jet combined with ab initio calculations. The structure of the only observed conformer of saligenin corresponds to the global minimum on the conformational surface. The observed structure is stabilized by an intramolecular strong O-H···O hydrogen bonding as well as a very weak O-H···π interaction. The hydrogen bond is formed through phenolic OH as the hydrogen bond donor and benzylic OH as the hydrogen bond acceptor while the O-H···π interaction is through benzylic O-H as the hydrogen bond donor and phenyl group as the hydrogen bond acceptor. It has been observed that the benzylic OH stretching frequency in saligenin is more red-shifted compared to that in benzyl alcohol as the strong O-H···O interaction present in saligenin acts on the benzylic O-H group. In fact, there is a subtle interplay among the strong O-H···O hydrogen bond, weak O-H···π interaction, and steric effects arising from the ortho substitution of the OH group in benzyl alcohol. This fine-tuning of multiple interactions very often governs the specific structures of biomolecules and materials. PMID:25010147

  6. Atmospheric pressure and temperature profiling using near IR differential absorption lidar

    NASA Technical Reports Server (NTRS)

    Korb, C. L.; Schwemmer, G. K.; Dombrowski, M.; Weng, C. Y.

    1983-01-01

    The present investigation is concerned with differential absorption lidar techniques for remotely measuring the atmospheric temperature and pressure profile, surface pressure, and cloud top pressure-height. The procedure used in determining the pressure is based on the conduction of high-resolution measurements of absorption in the wings of lines in the oxygen A band. Absorption with respect to these areas is highly pressure sensitive in connection with the mechanism of collisional line broadening. The method of temperature measurement utilizes a determination of the absorption at the center of a selected line in the oxygen A band which originates from a quantum state with high ground state energy.

  7. Study of the processes of carbonization and oxidation of porous silicon by Raman and IR spectroscopy

    SciTech Connect

    Vasin, A. V.; Okholin, P. N.; Verovsky, I. N.; Nazarov, A. N.; Lysenko, V. S.; Kholostov, K. I. Bondarenko, V. P.; Ishikawa, Y.

    2011-03-15

    Porous silicon layers were produced by electrochemical etching of single-crystal silicon wafers with the resistivity 10 {Omega} cm in the aqueous-alcohol solution of hydrofluoric acid. Raman spectroscopy and infrared absorption spectroscopy are used to study the processes of interaction of porous silicon with undiluted acetylene at low temperatures and the processes of oxidation of carbonized porous silicon by water vapors. It is established that, even at the temperature 550 Degree-Sign C, the silicon-carbon bonds are formed at the pore surface and the graphite-like carbon condensate emerges. It is shown that the carbon condensate inhibits oxidation of porous silicon by water vapors and contributes to quenching of white photoluminescence in the oxidized carbonized porous silicon nanocomposite layer.

  8. s-SNOM based IR and THz spectroscopy for nanoscale material characterization

    NASA Astrophysics Data System (ADS)

    Gokus, Tobias; Huber, Andreas; Cernescu, Adrian

    Scattering-type Scanning Near-field Optical Microscopy (s-SNOM) allows to overcome the diffraction limit of conventional light microscopy enabling optical measurements at a spatial resolution of 10nm. s-SNOM employs an externally-illuminated sharp metallic AFM tip to create a nanoscale hot-spot at its apex. The optical tip-sample near-field interaction is determined by the local dielectric properties (refractive index) of the sample and detection of the elastically tip-scattered light yields nanoscale resolved near-field images simultaneous to topography. Development of a dedicated Fourier-transform detection module for analyzing light scattered from the tip which is illuminated by a broadband laser source enables IR spectroscopy of complex polymer nanostructures. Applications presented further demonstrate characterization of embedded structural phases in biominerals (bone), organic semiconductors or functional semiconductor nanostructures.Furthermore, by extending the concept of broadband-s-SNOM spectroscopy to the THz-spectral range, we demonstrate optical near-field imaging and spectroscopy at THz-frequencies (0.5-2.5 THz) by coupling the free space beam of a dedicated THz-TDS to the s-SNOM system.

  9. Resonant IR multi-photon dissociation spectroscopy of a trapped and sympathetically cooled biomolecular ion species.

    PubMed

    Wellers, Ch; Borodin, A; Vasilyev, S; Offenberg, D; Schiller, S

    2011-11-14

    In this work we demonstrate vibrational spectroscopy of polyatomic ions that are trapped and sympathetically cooled by laser-cooled atomic ions. We use the protonated dipeptide tryptophan-alanine (HTyrAla(+)) as a model system, cooled by barium ions to less than 800 mK secular temperature. The spectroscopy is performed on the fundamental vibrational transition of a local vibrational mode at 2.74 μm using a continuous-wave optical parametric oscillator (OPO). Resonant IR multi-photon dissociation spectroscopy (R-IRMPD) (without the use of a UV laser) generates charged molecular fragments, which are sympathetically cooled and trapped, and subsequently released from the trap and counted. We measured the cross section for R-IRMPD under conditions of low intensity, and found it to be approximately two orders smaller than the vibrational excitation cross section. The observed rotational bandwidth of the vibrational transition is larger than the one expected from the combined effects of 300 K black-body temperature, conformer-dependent line shifts, and intermolecular vibrational relaxation broadening (J. Stearns et al., J. Chem. Phys., 2007, 127, 154322-154327). This indicates that as the internal energy of the molecule grows, an increase of the rotational temperature of the molecular ions well above room temperature (up to on the order of 1000 K), and/or an appreciable shift of the vibrational transition frequency (approx. 6-8 cm(-1)) occurs. PMID:21971203

  10. Direct and quantitative broadband absorptance spectroscopy with multilayer cantilever probes

    SciTech Connect

    Hsu, Wei-Chun; Tong, Jonathan Kien-Kwok; Liao, Bolin; Chen, Gang

    2015-04-21

    A system for measuring the absorption spectrum of a sample is provided that includes a broadband light source that produces broadband light defined within a range of an absorptance spectrum. An interferometer modulates the intensity of the broadband light source for a range of modulation frequencies. A bi-layer cantilever probe arm is thermally connected to a sample arm having at most two layers of materials. The broadband light modulated by the interferometer is directed towards the sample and absorbed by the sample and converted into heat, which causes a temperature rise and bending of the bi-layer cantilever probe arm. A detector mechanism measures and records the deflection of the probe arm so as to obtain the absorptance spectrum of the sample.

  11. Review on VUV to MIR absorption spectroscopy of atmospheric pressure plasma jets

    NASA Astrophysics Data System (ADS)

    Reuter, Stephan; Santos Sousa, Joao; Stancu, Gabi Daniel; Hubertus van Helden, Jean-Pierre

    2015-10-01

    Absorption spectroscopy (AS) represents a reliable method for the characterization of cold atmospheric pressure plasma jets. The method’s simplicity stands out in comparison to competing diagnostic techniques. AS is an in situ, non-invasive technique giving absolute densities, free of calibration procedures, which other diagnostics, such as laser-induced fluorescence or optical emission spectroscopy, have to rely on. Ground state densities can be determined without the knowledge of the influence of collisional quenching. Therefore, absolute densities determined by absorption spectroscopy can be taken as calibration for other methods. In this paper, fundamentals of absorption spectroscopy are presented as an entrance to the topic. In the second part of the manuscript, a review of AS performed on cold atmospheric pressure plasma jets, as they are used e.g. in the field of plasma medicine, is presented. The focus is set on special techniques overcoming not only the drawback of spectrally overlapping absorbing species, but also the line-of-sight densities that AS usually provides or the necessity of sufficiently long absorption lengths. Where references are not available for measurements on cold atmospheric pressure plasma jets, other plasma sources including low-pressure plasmas are taken as an example to give suggestions for possible approaches. The final part is a table summarizing examples of absorption spectroscopic measurements on cold atmospheric pressure plasma jets. With this, the paper provides a ‘best practice’ guideline and gives a compendium of works by groups performing absorption spectroscopy on cold atmospheric pressure plasma jets.

  12. Analysis of functional groups in atmospheric aerosols by infrared spectroscopy: sparse methods for statistical selection of relevant absorption bands

    NASA Astrophysics Data System (ADS)

    Takahama, Satoshi; Ruggeri, Giulia; Dillner, Ann M.

    2016-07-01

    Various vibrational modes present in molecular mixtures of laboratory and atmospheric aerosols give rise to complex Fourier transform infrared (FT-IR) absorption spectra. Such spectra can be chemically informative, but they often require sophisticated algorithms for quantitative characterization of aerosol composition. Naïve statistical calibration models developed for quantification employ the full suite of wavenumbers available from a set of spectra, leading to loss of mechanistic interpretation between chemical composition and the resulting changes in absorption patterns that underpin their predictive capability. Using sparse representations of the same set of spectra, alternative calibration models can be built in which only a select group of absorption bands are used to make quantitative prediction of various aerosol properties. Such models are desirable as they allow us to relate predicted properties to their underlying molecular structure. In this work, we present an evaluation of four algorithms for achieving sparsity in FT-IR spectroscopy calibration models. Sparse calibration models exclude unnecessary wavenumbers from infrared spectra during the model building process, permitting identification and evaluation of the most relevant vibrational modes of molecules in complex aerosol mixtures required to make quantitative predictions of various measures of aerosol composition. We study two types of models: one which predicts alcohol COH, carboxylic COH, alkane CH, and carbonyl CO functional group (FG) abundances in ambient samples based on laboratory calibration standards and another which predicts thermal optical reflectance (TOR) organic carbon (OC) and elemental carbon (EC) mass in new ambient samples by direct calibration of infrared spectra to a set of ambient samples reserved for calibration. We describe the development and selection of each calibration model and evaluate the effect of sparsity on prediction performance. Finally, we ascribe

  13. Cold, Gas-Phase UV and IR Spectroscopy of Protonated Leucine Enkephalin and its Analogues

    NASA Astrophysics Data System (ADS)

    Burke, Nicole L.; Redwine, James; Dean, Jacob C.; McLuckey, Scott A.; Zwier, Timothy S.

    2014-06-01

    The conformational preferences of peptide backbones and the resulting hydrogen bonding patterns provide critical biochemical information regarding the structure-function relationship of peptides and proteins. The spectroscopic study of cryogenically-cooled peptide ions in a mass spectrometer probes these H-bonding arrangements and provides information regarding the influence of a charge site. Leucine enkephalin, a biologically active endogenous opiod peptide, has been extensively studied as a model peptide in mass spectrometry. This talk will present a study of the UV and IR spectroscopy of protonated leucine enkephalin [YGGFL+H]+ and two of its analogues: the sodiated [YGGFL+Na]+ and C-terminally methyl esterified [YGGFL-OMe+H]+ forms. All experiments were performed in a recently completed multi-stage mass spectrometer outfitted with a cryocooled ion trap. Ions are generated via nano-electrospray ionization and the analyte of interest is isolated in a linear ion trap. The analyte ions are trapped in a 22-pole ion trap held at 5 K by a closed cycle helium cryostat and interrogated via UV and IR lasers. Photofragments are trapped and isolated in a second LIT and mass analyzed. Double-resonance UV and IR methods were used to assign the conformation of [YGGFL+H]+, using the NH/OH stretch, Amide I, and Amide II regions of the infrared spectrum. The assigned structure contains a single backbone conformation at vibrational/rotational temperatures of 10 K held together with multiple H-bonds that self-solvate the NH3+ site. A "proton wire" between the N and C termini reinforces the H-bonding activity of the COO-H group to the F-L peptide bond, whose cleavage results in formation of the b4 ion, which is a prevalent, low-energy fragmentation pathway for [YGGFL+H]+. The reinforced H-bonding network in conjunction with the mobile proton theory may help explain the prevalence of the b4 pathway. In order to elucidate structural changes caused by modifying this H-bonding activity

  14. IR spectroscopy of ethanol in nitrogen cryomatrices with different concentration ratios

    NASA Astrophysics Data System (ADS)

    Aldiyarov, A.; Aryutkina, M.; Drobyshev, A.; Kurnosov, V.

    2011-06-01

    Thin films of cryovacuum condensates of ethanol-nitrogen mixtures formed by co-condensation of gas mixtures with different concentrations on a cooled metal substrate are studied by IR spectrometry. The condensation temperature was Tc = 16 K and the pressure of the gaseous phase during cryodeposition was P = 10-5 Torr. The ethanol concentration in nitrogen was varied from 0.5 to 10% and the film thickness, from 1 to 30 μm. Measurements were made in the range from 400 to 4200 cm-1. An analysis of the IR spectra and a comparison with published data shows that ethanol monomers and dimers are present in the nitrogen matrix. This is indicated by an absorption band at a frequency of 3658 cm-1 owing to vibrations of O-H bonds of ethanol monomers and dimers. The local minima of this band at 3645 and 3658 cm-1 are related to the existence of two conformational states of the ethanol molecule: anti (3658 cm-1) and gauche (3645 cm-1). In addition, the presence of ethanol dimers and monomers in the matrix leads to the appearance of absorption bands at 1259 and 1276 cm-1 attributable to deformation vibrations δ(COH) of the anti- and gauche-isomers, respectively, as well as bands corresponding to a combination of ν(CCO) valence vibrations and rotational oscillations of the methyl group r(CH3) attributable to anti-dimers (ν = 1090 cm-1) and anti-monomers (ν = 1095 cm-1). Local minima within 3000-3600 cm-1 also indicate the presence of cyclical dimers, trimers, and tetramers, as well as hexamers in the matrix. A broad band over 3250-3330 cm-1 indicates that large polyaggregates, with ethanol molecules in a hydrogen-bond state (multimer), exist in the matrix.

  15. The hydration dependence of CaCO3 absorption lines in the Far IR

    NASA Astrophysics Data System (ADS)

    Powell, Johnny; Emery, Logan P

    2014-06-01

    The far infrared (FIR) absorption lines of CaCO3 have been measured at a range of relative humidities (RH) between 33 and 92% RH using a Bruker 66v/S spectrometer. Hydration measurements on CaCO3 have been made in the mid-infrared (MIR) by [Al-Hosney, H.A. and Grassian, V.H., 2005, Phys. Chem. Chem. Phys., 7, 1266], and astrophysically-motivated temperature-dependent FIR measurements of CaCO3 in vacuum have also been reported [Posch, T., et al., 2007, Ap. J., 668, 993]. The custom sample cell constructed for these hydrated-FIR spectra is required because the 66v/S bench is under vacuum (3 mbar) during typical measurements. Briefly, the sample cell consists of two Thalium Bromoiodide (KRS-5) windows, four O-rings, a plastic ring for separating the windows and providing a volume for the saturated atmosphere. CaCO3 was deposited on KRS-5 windows using doubly-distilled water as an intermediary. The KRS-5 window with sample and assembled sample cell were placed in a desiccator with the appropriated saturated salt solution [Washburn, E.W. (Ed.), International Critical Tables of Numerical Data, Physics Chemistry and Technology, Vol. 1, (McGraw-Hill, New York, 1926), p. 67-68] and allowed to hydrate for 23 hours. For spectroscopy the desiccator was quickly opened and the second KRS-5 window placed in the cell to seal the chamber. A spectrum was then taken of the sample at the appropriate RH. The spectra taken characterize the adsorption of water vapor and CaCO3 that might occur in circumstellar environments [Melnick, G.J., et al. 2001, Nature, 412, 160].The MIR and FIR reflectance spectra of calcite (CaCO3) have been thoroughly studied by [Hellwege, K.H., et al., 1970, Z. Physik, 232, 61]. Five Lorentzian curves were fit to our data in the range from 378-222 cm-1/SUP> and each was able to be assigned to a known mode of CaCO3. The data does not support the conclusion of a hydration effect on these modes of CaCO3, but it does suggest a possible broadening of three modes

  16. All solid-state mid-IR laser development, nonlinear absorption investigation and laser-induced damage study

    NASA Astrophysics Data System (ADS)

    Wagner, Torrey J.

    In this research, nonlinear optical absorption coefficients and laser-induced damage thresholds are measured in Ge and GaSb, which are materials that are used in IR detectors. Using a simultaneous fitting technique to extract nonlinear absorption coefficients from data at two pulse widths, two-photon and free-carrier absorption coefficients are measured in Ge and GaSb at 2.05 and 2.5 mum for the first time. At these wavelengths, nonlinear absorption is the primary damage mechanism, and damage thresholds at picosecond and nanosecond pulse widths were measured and agreed well with modeled thresholds using experimentally measured parameters. The damage threshold for a single-layer Al2O 3 anti-reflective coating on Ge was 55% or 35% lower than the uncoated threshold for picosecond or nanosecond pulses, respectively. It was necessary to develop a pulsed 2.5 mum wavelength laser to conduct these measurements, as prior lasers at this wavelength possessed insufficient pulse energy to induce nonlinear absorption or damage these materials. Using a Cr2+ :ZnSe gain medium, a 3.1 mJ pulse energy laser was created whose peak power exceeded all Cr2+:ZnSe literature by a factor of eight. The characteristics of the laser include nanosecond pulse width, 52% slope efficiency, beam quality of M2 = 1.4, Gaussian spatial profile and a spectral line width of 110 nm.

  17. Experimental implementations of 2D IR spectroscopy through a horizontal pulse shaper design and a focal plane array detector.

    PubMed

    Ghosh, Ayanjeet; Serrano, Arnaldo L; Oudenhoven, Tracey A; Ostrander, Joshua S; Eklund, Elliot C; Blair, Alexander F; Zanni, Martin T

    2016-02-01

    Aided by advances in optical engineering, two-dimensional infrared spectroscopy (2D IR) has developed into a promising method for probing structural dynamics in biophysics and material science. We report two new advances for 2D IR spectrometers. First, we report a fully reflective and totally horizontal pulse shaper, which significantly simplifies alignment. Second, we demonstrate the applicability of mid-IR focal plane arrays (FPAs) as suitable detectors in 2D IR experiments. FPAs have more pixels than conventional linear arrays and can be used to multiplex optical detection. We simultaneously measure the spectra of a reference beam, which improves the signal-to-noise by a factor of 4; and two additional beams that are orthogonally polarized probe pulses for 2D IR anisotropy experiments. PMID:26907414

  18. 2D IR spectroscopy at 100 kHz utilizing a Mid-IR OPCPA laser source.

    PubMed

    Luther, Bradley M; Tracy, Kathryn M; Gerrity, Michael; Brown, Susannah; Krummel, Amber T

    2016-02-22

    We present a 100 kHz 2D IR spectrometer. The system utilizes a ytterbium all normal dispersion fiber oscillator as a common source for the pump and seed beams of a MgO:PPLN OPCPA. The 1030 nm OPCPA pump is generated by amplification of the oscillator in cryocooled Yb:YAG amplifiers, while the 1.68 μm seed is generated in a OPO pumped by the oscillator. The OPCPA outputs are used in a ZGP DFG stage to generate 4.65 μm pulses. A mid-IR pulse shaper delivers pulse pairs to a 2D IR spectrometer allowing for data collection at 100 kHz. PMID:26907062

  19. An Ion’s Perspective on the Molecular Motions of Nano-confined Water: A 2D IR Spectroscopy Study

    PubMed Central

    Singh, Prabhat K; Kuroda, Daniel G.; Hochstrasser, Robin M.

    2013-01-01

    The vibrational population relaxation and the hydration shell dynamics of the symmetric tricyanomethanide (TCM) anion is investigated in AOT reverse micelle as a function of the water pool radius. Two-dimensional infrared spectroscopy in combination with linear absorption and ultrafast IR pump-probe spectroscopy is utilized in this study. Spectroscopic measurements show that the anion has two bands in the 2160 – 2175 cm−1 region, each with its own spectroscopic signatures. Analysis of the vibrational dynamics shows that the two vibrational bands are consistent with the anion located either at the interface or in the water pool. The sensitivity of the TCM anion to the environment allows us to unequivocally monitor the vibrational and hydration dynamics of the anion in those two different environments. TCM anion located at the interface does not show any significant variation of the vibrational dynamics with the water pool size. On the contrary, the TCM anion inside the water pool exhibits a large and non-linear variation of the vibrational lifetime and the frequency-frequency correlation time with the pool radius. Moreover for the solvated anion in water pools of 49 Å in radius (W0=30), the vibrational lifetime reaches the values observed for the anion in bulk water while the frequency-frequency correlation time shows a characteristic time higher than that observed in the bulk. In addition, for the first time a model is developed and used to explain the observed non-linear variation of the spectroscopic observables with the pool size. This model attributes the changes in the vibrational dynamics of the TCM anion in the water pool to the slow and radius dependent water dynamics present in the confined environment of a reverse micelle. PMID:23855349

  20. Mid-IR Photometry and Near-IR Spectroscopy of the FU Ori Protostar V2775 Ori (HOPS 223)

    NASA Astrophysics Data System (ADS)

    Fischer, William J.; Safron, Emily J.; Megeath, S. Thomas; Terebey, Susan; Soto, Edith; Wilson, Thomas L.; Adams, Joseph D.

    2016-02-01

    On 2015 November 20.39, we obtained mid-IR photometry of V2775 Ori (HOPS 223) with the FORCAST instrument aboard SOFIA. This is a low-mass embedded young stellar object that was reported to have undergone a luminosity outburst by Caratti o Garatti et al. (2011, A & A, 526, L1). Fischer et al. (2012, ApJ, 756, 99) dated the beginning of the outburst to between 2005 April and 2007 March and discussed the similarity of its near-IR spectrum to that of FU Orionis.

  1. Diamond-like carbon films for polyethylene femoral parts: Raman and FT-IR spectroscopy before and after incubation in simulated body liquid.

    PubMed

    Dorner-Reisel, A; Gärtner, G; Reisel, G; Irmer, G

    2008-03-01

    In artificial prosthetics for knee, hip, finger or shoulder joints, ultrahigh molecular weight polyethylene (UHMW-PE) is a significant material. Several attempts to reduce the wear rate of UHMW-PE, i.e. the application of suitable coatings, are in progress. A surface modification of polyethylene with wear-resistant hydrogenated diamond-like carbon is favourable, owing to the chemical similarity of polyethylene (-C-H(2)-)(n) and C:H or amorphous C:H (a-C:H) coatings with diamond-like properties. In the present study, the microstructure of a-C:H coatings on UHMW-PE substrates was investigated by Raman and Fourier transform infrared (FT-IR) spectroscopy. FT-IR spectroscopy shows very broad absorption lines, which point to the disorder and diversity of different symmetric, asymmetric aromatic, olefin sp(2)-hybridized or sp(3)-hybridized C-H groups in the amorphous diamond-like carbon coating. Following a long incubation of 12 months in a simulated body liquid, the structural investigations were repeated. Furthermore, fractured cross-sections and the wetting behaviour with polar liquids were examined. After incubation in simulated body liquid, Raman spectroscopy pointed to a reduction of the C-H bonds in the diamond-like carbon coatings. On the basis of these findings, one can conclude that hydrogenated diamond-like carbon is able to interact with salt solutions by substituting the hydrogen with appropriate ions. PMID:18157668

  2. Solution Structure of Azidoalcohols Studied by IR Spectroscopy and Quantum Chemistry

    NASA Astrophysics Data System (ADS)

    Karpov, S. V.; Lodygina, V. P.; Malkov, G. V.

    2014-03-01

    Features of the association of azidoalcohols in CH2Cl2 were studied by IR spectroscopy using 1,3-diazidopropan-2-ol and 1-azidoethan-2-ol as examples. It was established that the investigated compounds could exist as two types of [OH…N3] associates. In the fi rst instance, the OH group was affected by strong intermolecular interactions like in common alcohols; in the second, the interactions were much weaker. Density functional theory and quantum theory of atoms-in-molecules were used to determine the structures of such associates and the energy parameters of the observed intermolecular interactions. Also, the experimental and calculated frequencies of OH stretching vibrations were correlated.

  3. Near-IR Spectroscopy of CEMP Stars with SOAR/OSIRIS

    NASA Astrophysics Data System (ADS)

    Kennedy, Catherine R.; Sivarani, T.; Beers, T.; Rossi, S.; Placco, V.; Johnson, J.; Masseron, T.

    2009-01-01

    We report on medium-resolution near-IR spectroscopy of a sample of over 70 Carbon-Enhanced Metal-Poor (CEMP) stars observed with SOAR/OSIRIS, selected from the HK survey of Beers and colleagues and the Hamburg/ESO Survey of Christlieb and colleagues. Oxygen abundances from the molecular CO lines as well as 12C/13C ratios are estimated from the near-IR spectra of these stars. Near-IR model spectra with varying oxygen abundances, in combination with previously determined parameters from optical spectra, are used for the estimation of abundances for this sample. There are two categories of CEMP stars: those with neutron-capture enhancement (CEMP-s, CEMP-r, CEMP-r/s), and those without (CEMP-no). Abundance patterns of those stars with neutron-capture enhancement are posited to be the result of mass transer from AGB companion stars. The origin of the abundance patterns in CEMP-no stars is less certain. Proposed models include low-metallicity AGB mass-transfer (in which the s-process is supressed), mass loss by rapidly rotating mega metal-poor stars ([Fe/H]< -6.0), or pollution by early supernovae. As both oxygen abundances and 12C/13C ratios are tracers of nucleosynthesis, we hope to gain information about Galactic nucleosynthesis through the analysis of this sample. This work was supported in part by grants PHY 02-16783 and PHY 08-22648: Physics Frontiers Center / Joint Institute for Nuclear Astrophysics (JINA), awarded by the U.S. National Science Foundation.

  4. Quantitative FT-IR spectroscopy of gypsum raw material for industry

    NASA Astrophysics Data System (ADS)

    Schwendtner, K.; Libowitzky, E.; Götzinger, M. A.; Koss, S.

    2003-04-01

    Today quality control (QC) is a big issue for being competitive in the gypsum industry. Knowledge and understanding of the raw material help to enhance the quality and permanence of products. Therefore a rapid, precise and user-friendly FT-IR spectroscopic method for quantitative analysis of gypsum, anhydrite, magnesite and dolomite from the gypsum deposit of Puchberg, Austria is being developed. There are decisive advantages of FT-IR spectroscopy compared to thermogravimetric methods (TG, DTA, DSC) or XRD, which are commonly used for QC, e.g. it is frequently available in industry labs and a spectrum can be obtained in a few minutes, with a minimum of sample preparation. The effects of particle size and ratio of dilution with KBr were investigated in transmission mode, using KBr pellets, as well as in diffuse reflexion mode. Little differences in particle size lead to enormous differences in peak height in transmission mode, but show only little effects in diffuse reflexion. The small amounts of sample used in KBr pellets (e.g. 2 mg sample : 500 mg KBr) also turned out to be disadvantageous, just like the time consuming sample preparation. Measurements in diffuse reflexion with a sample to KBr ratio of 1:10 show promising results for use in standardization, whereas higher dilutions hardly improve the quality, and ratios of 1:5 still show components of specular reflection. The calibration model for quantitative analysis is being constructed measuring various defined mixtures of >98% pure natural minerals (gypsum, magnesite, dolomite), and synthetic materials (anhydrite). The latter was obtained by heating gypsum at 350^oC for 10 h. The synthetic material was chosen, because natural material was not available in sufficient amounts with high purity. The IR method is compared with results achieved with XRD-Rietveld and thermogravimetric methods. Advantages of chemometrical software based on multivariate statistical techniques will be investigated and compared with

  5. [The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

    PubMed

    Zhang, Li-fang; Wang, Fei; Yu, Li-bin; Yan, Jian-hua; Cen, Ke-fa

    2015-06-01

    In order to on-line measure the trace ammonia slip of the commercial power plant in the future, this research seeks to measure the trace ammonia by using tunable diode laser absorption spectroscopy under ambient temperature and pressure, and at different temperatures, and the measuring temperature is about 650 K in the power plant. In recent years lasers have become commercially available in the near-infrared where the transitions are much stronger, and ammonia's spectroscopy is pretty complicated and the overlapping lines are difficult to resolve. A group of ammonia transitions near 4 433.5 cm(-1) in the v2 +v3 combination band have been thoroughly selected for detecting lower concentration by analyzing its absorption characteristic and considering other absorption interference in combustion gases where H2O and CO2 mole fraction are very large. To illustrate the potential for NH3 concentration measurements, predictions for NH3, H2O and CO2 are simultaneously simulated, NH3 absorption lines near 4 433.5 cm(-1) wavelength meet weaker H2O absorption than the commercial NH3 lines, and there is almost no CO2 absorption, all the parameters are based on the HITRAN database, and an improved detection limit was obtained for interference-free NH3 monitoring, this 2.25 μm band has line strengths several times larger than absorption lines in the 1.53 μm band which was often used by NH3 sensors for emission monitoring and analyzing. The measurement system was developed with a new Herriott cell and a heated gas cell realizing fast absorption measurements of high resolution, and combined with direct absorption and wavelenguh modulation based on tunable diode laser absorption spectroscopy at different temperatures. The lorentzian line shape is dominant at ambient temperature and pressure, and the estimated detectivity is approximately 0.225 x 10(-6) (SNR = 1) for the directed absorption spectroscopy, assuming a noise-equivalent absorbance of 1 x 10(-4). The heated cell

  6. gamma-Irradiation effects on the thermal decomposition behaviour and IR absorption spectra of piperacillin

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Gaffar, M. A.; Abu El-Fadl, A.; Hamad, Ar. G. K.

    2003-11-01

    The thermal decomposition behaviour of unirradiated and pre-gamma-irradiated piperacillin (pipril) as a semi-synthetic penicillin antibiotic has been studied in the temperature range of (273-1072 K). The decomposition was found to proceed through three major steps both for unirradiated and gamma-irradiated samples. Neither appearance nor disappearance of new bands in the IR spectrum of piperacillin was recorded as a result of gamma-irradiation but only a decrease in the intensity of most bands was observed. A degradation mechanism was suggested to explain the bond rupture and the decrease in the intensities of IR bands of gamma-irradiated piperacillin.

  7. Defect sites in highly siliceous HZSM-5 zeolites: A study performed by alumination and IR spectroscopy

    SciTech Connect

    Yamagishi, Kouji; Namba, Seitaro; Yashima, Tatsuaki )

    1991-01-24

    The concentration of oxygen atoms on defect sites in a highly siliceous HZSM-5 type zeolite was estimated by the {sup 18}O-exchange reaction between C{sup 18}O{sub 2} and the zeolite. The concentration of oxygen atoms on defect sites could be controlled by means of changes of the gel composition and of the use of various silica sources in the hydrothermal synthesis. The relationship between the concentration of oxygen atoms on defect sites in a highly siliceous HZSM-5 and the concentration of aluminum introduced into the framework of the HZSM-5 by an alumination was examined. The concentration of the framework aluminum was the same as one-fourth that of the oxygen atoms on defect sites. These results suggest that the defect sites into which aluminum atoms are introduced tetrahedrally can be identified with hydroxyl nests that consist of four silanol groups. The existence of hydroxyl nests could be confirmed by IR spectroscopy. From the {sup 18}O-exchange reaction and IR measurements, the authors conclude that the sharp band at 3,740 cm{sup {minus}1} can be attributed to both isolated SiOH groups on the external surface and intracrystalline isolated SiOH groups and that the broad band at 3,505 cm{sup {minus}1} can be attributed to the SiOH groups in hydroxyl nests.

  8. Identification of forged Bank of England £20 banknotes using IR spectroscopy.

    PubMed

    Sonnex, Emily; Almond, Matthew J; Baum, John V; Bond, John W

    2014-01-24

    Bank of England notes of £20 denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. An aim of this work was to develop a non-destructive method so that a small, compact Fourier transform infrared spectrometer (FT-IR) instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 cm(-1) arising from νasym (CO3(2-)) from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine £20 notes were observed in the ν(OH) (ca. 3500 cm(-1)), ν(C-H) (ca. 2900 cm(-1)) and ν(C=O) (ca. 1750 cm(-1)) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper. PMID:24176248

  9. Identification of forged Bank of England £20 banknotes using IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sonnex, Emily; Almond, Matthew J.; Baum, John V.; Bond, John W.

    2014-01-01

    Bank of England notes of £20 denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. An aim of this work was to develop a non-destructive method so that a small, compact Fourier transform infrared spectrometer (FT-IR) instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 cm-1 arising from νasym (CO32-) from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine £20 notes were observed in the ν(OH) (ca. 3500 cm-1), ν(Csbnd H) (ca. 2900 cm-1) and ν(Cdbnd O) (ca. 1750 cm-1) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper.

  10. Study of rare-earth fluoride oxalate tetrahydrates by IR spectroscopy

    SciTech Connect

    Pushkina, G.Ya.; Kizhlo, M.R.; Komissarova, L.N.; Shatskii, V.M.

    1987-01-01

    The IR spectra of ..cap alpha..-LnC/sub 2/O/sub 4/F x 4H/sub 2/O (Ln = Tb, Dy, Ho, Y) and ..beta..-LnC/sub 2/O/sub 4/F x 4H/sub 2/O (Ln = Tb-Lu, Y) and their deuteration products have been studied. The structural features of these fluoride oxalate tetrahydrates have been discussed on the basis of a comparison of data from IR and PMR spectroscopy and a complex thermal analysis. It has been shown that the ..cap alpha.. and ..beta.. modifications differ with respect to the coordination of the water molecules. In ..beta..-LnC/sub 2/O/sub 4/F x 4H/sub 2/O two H/sub 2/O molecules are coordinated by the metal, and the remaining water participates in the creation of a system of strong hydrogen bonds. In ..cap alpha..-LnC/sub 2/O/sub 4/F x 4H/sub 2/O the character of the coordination of the H/sub 2/O molecules is more complicated, at least three different types of water molecules can be identified, and more than two water molecules are probably coordinated by the metal. The type of coordination of the oxalato groups in the compounds has been discussed.

  11. Studies of Arctic Middle Atmosphere Chemistry using Infrared Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lindenmaier, Rodica

    The objective of this Ph.D. project is to investigate Arctic middle atmosphere chemistry using solar infrared absorption spectroscopy. These measurements were made at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, which is operated by the Canadian Network for the Detection of Atmospheric Change (CANDAC). This research is part of the CANDAC/PEARL Arctic Middle Atmosphere Chemistry theme and aims to improve our understanding of the processes controlling the stratospheric ozone budget using measurements of the concentrations of stratospheric constituents. The instrument, a Bruker IFS 125HR Fourier transform infrared (FTIR) spectrometer, has been specifically designed for high-resolution measurements over a broad spectral range and has been used to measure reactive species, source gases, reservoirs, and dynamical tracers at PEARL since August 2006. The first part of this research focuses on the optimization of ozone retrievals, for which 22 microwindows were studied and compared. The spectral region from 1000 to 1005 cm-1 was found to be the most sensitive in both the stratosphere and troposphere, giving the highest number of independent pieces of information and the smallest total error for retrievals at Eureka. Similar studies were performed in coordination with the Network for the Detection of Atmospheric Composition Change for nine other species, with the goal of improving and harmonizing the retrieval parameters among all Infrared Working Group sites. Previous satellite validation exercises have identified the highly variable polar conditions of the spring period to be a challenge. In this work, comparisons between the 125HR and ACE-FTS (Atmospheric Chemistry Experiment-Fourier transform spectrometer) from 2007 to 2010 have been used to develop strict criteria that allow the ground and satellite-based instruments to be confidently compared. After applying these criteria, the differences between the two instruments were generally

  12. X-ray absorption spectroscopy of chicken sulfite oxidase crystals

    SciTech Connect

    George, G.N.; Pickering, I.J.; Kisker, C.

    1999-05-17

    Sulfite oxidase catalyzes the physiologically vital oxidation of sulfite to sulfate. Recently, the crystal structure of chicken sulfite oxidase has been reported at 1.9 {angstrom} resolution. In contrast to the information available from previous X-ray absorption spectroscopic studies, the active site indicated by crystallography was a mono-oxo species. Because of this the possibility that the crystals did in fact contain a reduced molybdenum species was considered in the crystallographic work. The authors report herein an X-ray absorption spectroscopic study of polycrystalline sulfite oxidase prepared in the same manner as the previous single-crystal samples, and compare this with data for frozen solutions of oxidized and reduced enzyme.

  13. Limiting resolution of linear absorption spectroscopy in thin gas cells

    NASA Astrophysics Data System (ADS)

    Izmailov, A. Ch.

    2010-06-01

    The most narrow sub-Doppler frequency resonances in the linear absorption of monochromatic radiation that propagates in the normal direction through a cell containing a layer of rarefied gas medium with a thickness smaller than or on the order of the wavelength of this radiation are theoretically studied. The calculation is performed using as an example a three-dimensional gas cell shaped like a rectangular parallelepiped. It is shown that the width and amplitude of considered sub-Doppler resonances (in the vicinity of centers of rather weak quantum transitions) significantly depend on the transit relaxation of atomic particles, which is determined by their transit times through the irradiated region of the cell both in longitudinal and in transverse directions. The restrictions of the approximation of the planar one-dimensional cell that was previously used in such calculations are determined. Possible applications of linear absorption resonances in ultrathin (nanometer) gas cells as references for optical frequency standards are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  15. Time-resolved pump and probe x-ray absorption fine structure spectroscopy at beamline P11 at PETRA III.

    PubMed

    Göries, D; Dicke, B; Roedig, P; Stübe, N; Meyer, J; Galler, A; Gawelda, W; Britz, A; Geßler, P; Sotoudi Namin, H; Beckmann, A; Schlie, M; Warmer, M; Naumova, M; Bressler, C; Rübhausen, M; Weckert, E; Meents, A

    2016-05-01

    We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy)3. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM). PMID:27250401

  16. Nonlinear absorption and transmission properties of Ge, Te and InAs using tuneable IR FEL

    SciTech Connect

    Amirmadhi, F.; Becker, K.; Brau, C.A.

    1995-12-31

    Nonlinear absorption properties of Ge, Te and InAs are being investigated using the transmission of FEL optical pulses through these semiconductors (z-scan method). Wavelength, intensity and macropulse dependence are used to differentiate between two-photon and free-carrier absorption properties of these materials. Macropulse dependence is resolved by using a Pockles Cell to chop the 4-{mu}s macropulse down to 100 ns. Results of these experiments will be presented and discussed.

  17. Analysis of a Brazilian baroque sculpture using Raman spectroscopy and FT-IR

    NASA Astrophysics Data System (ADS)

    Freitas, Renato P.; Ribeiro, Iohanna M.; Calza, Cristiane; Oliveira, Ana L.; Felix, Valter S.; Ferreira, Douglas S.; Pimenta, André R.; Pereira, Ronaldo V.; Pereira, Marcelo O.; Lopes, Ricardo T.

    2016-02-01

    In this study, samples were taken from the sculpture of Our Lady of Sorrows and analyzed by Raman spectroscopy and FT-IR. This sculpture has been dated to the early eighteenth century. Samples were also examined using optical microscopy and Energy Dispersive Spectroscopy (EDS). Based on chemical analysis, the pigments vermilion [HgS], massicot [PbO] and azurite [Cu3(CO3)2(OH)2] were found in the sculpture polychrome. The results indicate that the green polychrome of the sculpture's mantle comes from the blending of massicot and azurite. Because the literature reports that the mantle of the Our Lady of Sorrows sculpture is blue, the mixing of these pigments results from a production error. The results also indicate the presence of Au in the sculpture, which indicates the originality of the piece. The results from this study helped restorers to choose the appropriate procedures for intervening in the sculpture and contributed to the knowledge about the manufacturing process of Brazilian baroque sculptures.

  18. Development and testing of an image-guided FT-IR instrument for field spectroscopy

    NASA Astrophysics Data System (ADS)

    Dai, Xiaobing; Liu, Xiangyan; Liu, Li

    2015-09-01

    Standoff detection, identification and quantification of chemicals require sensitive spectrometers with calibration capabilities. We have developed a compact novel instrument that can not only provide imaging capability, bust also one that provides spectral capability of the field of view (FOV) center under the image-guided. The system employs a Fourier transform infrared (FT-IR) spectrometer, coupled with chalcogenide glass optical fiber, and a specially designed infrared optic lens. A special kit provided by Bruker Optics is connected on the spectrometer to focus the infrared beam from the lens at the entry of the fiber. Its spectral range covers the infrared band from 1850cm-1 to 5000cm-1 and its spectral resolution could be chosen among six selected values 1, 2, 4, 8, 16, 32cm-1. This paper will address the issues of image-guided spectroscopy and will show how an instrument designed for specifically imaging applications can dramatically improve the performance of the system and quality of the data acquired. The benefit of these technologies in spectroscopy can be demonstrated with a system optimally designed for detecting spectral characteristics of moving targets.

  19. Analysis of a Brazilian baroque sculpture using Raman spectroscopy and FT-IR.

    PubMed

    Freitas, Renato P; Ribeiro, Iohanna M; Calza, Cristiane; Oliveira, Ana L; Felix, Valter S; Ferreira, Douglas S; Pimenta, André R; Pereira, Ronaldo V; Pereira, Marcelo O; Lopes, Ricardo T

    2016-02-01

    In this study, samples were taken from the sculpture of Our Lady of Sorrows and analyzed by Raman spectroscopy and FT-IR. This sculpture has been dated to the early eighteenth century. Samples were also examined using optical microscopy and Energy Dispersive Spectroscopy (EDS). Based on chemical analysis, the pigments vermilion [HgS], massicot [PbO] and azurite [Cu3(CO3)2(OH)2]were found in the sculpture polychrome. The results indicate that the green polychrome of the sculpture's mantle comes from the blending of massicot and azurite. Because the literature reports that the mantle of the Our Lady of Sorrows sculpture is blue, the mixing of these pigments results from a production error. The results also indicate the presence of Au in the sculpture, which indicates the originality of the piece. The results from this study helped restorers to choose the appropriate procedures for intervening in the sculpture and contributed to the knowledge about the manufacturing process of Brazilian baroque sculptures. PMID:26513229

  20. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    SciTech Connect

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

    2007-08-02

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over 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. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

  1. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    NASA Astrophysics Data System (ADS)

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

    2007-08-01

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over 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. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

  2. 2D IR Spectroscopy using Four-Wave Mixing, Pulse Shaping, and IR Upconversion: A Quantitative Comparison

    PubMed Central

    Rock, William; Li, Yun-Liang; Pagano, Philip; Cheatum, Christopher M.

    2013-01-01

    Recent technological advances have led to major changes in the apparatuses used to collect 2D IR spectra. Pulse shaping offers several advantages including rapid data collection, inherent phase stability, and phase cycling capabilities. Visible array detection via upconversion allows the use of visible detectors that are cheaper, faster, more sensitive, and less noisy than IR detectors. However, despite these advantages, many researchers are reluctant to implement these technologies. Here we present a quantitative study of the S/N of 2D IR spectra collected with a traditional four-wave mixing (FWM) apparatus, with a pulse shaping apparatus, and with visible detection via upconversion to address the question of whether or not weak chromophores at low concentrations are still accessible with such an apparatus. We find that the enhanced averaging capability of the pulse shaping apparatus enables the detection of small signals that would be challenging to measure even with the traditional FWM apparatus, and we demonstrate this ability on a sample of cyanylated dihydrofolate reductase (DHFR). PMID:23687988

  3. Multinozzle supersonic expansion for Fourier transform absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Georges, R.; Durry, G.; Bach, M.; Pétrisse, R.; Jost, R.; Herman, M.

    1995-12-01

    A new supersonic expansion made of several, up to 31 aligned nozzles, on top of a set of powerful Roots blowers has been built. Adequate optics allowed the recording of infrared absorption spectra in a cell with a Fourier transform interferometer, at high spectral resolution. The system was tested with N 2O, between 2000 and 4800 cm -1. The ν1 + 2 ν2 + ν3 combination band, estimated to be some 10000 times weaker than the ν2 fundamental, could be observed among all the other expected bands, thus setting a limit for the sensitivity of the system. The formation of large N 2O clusters was observed.

  4. Absorption spectroscopy of a laboratory photoionized plasma experiment at Z

    SciTech Connect

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

    2014-03-15

    The Z facility at the Sandia National Laboratories is the most energetic terrestrial source of X-rays and provides an opportunity to produce photoionized plasmas in a relatively well characterised radiation environment. We use detailed atomic-kinetic and spectral simulations to analyze the absorption spectra of a photoionized neon plasma driven by the x-ray flux from a z-pinch. The broadband x-ray flux both photoionizes and backlights the plasma. In particular, we focus on extracting the charge state distribution of the plasma and the characteristics of the radiation field driving the plasma in order to estimate the ionisation parameter.

  5. Single-dot absorption spectroscopy and theory of silicon nanocrystals

    NASA Astrophysics Data System (ADS)

    Sychugov, Ilya; Pevere, Federico; Luo, Jun-Wei; Zunger, Alex; Linnros, Jan

    2016-04-01

    Photoluminescence excitation measurements have been performed on single, unstrained oxide-embedded Si nanocrystals. Having overcome the challenge of detecting weak emission, we observe four broad peaks in the absorption curve above the optically emitting state. Atomistic calculations of the Si nanocrystal energy levels agree well with the experimental results and allow identification of some of the observed transitions. An analysis of their physical nature reveals that they largely retain the indirect band-gap structure of the bulk material with some intermixing of direct band-gap character at higher energies.

  6. A GAS TEMPERATURE PROFILE BY INFRARED EMISSION-ABSORPTION SPECTROSCOPY

    NASA Technical Reports Server (NTRS)

    Buchele, D. R.

    1994-01-01

    This computer program calculates the temperature profile of a flame or hot gas. Emphasis is on profiles found in jet engine or rocket engine exhaust streams containing water vapor or carbon dioxide as radiating gases. The temperature profile is assumed to be axisymmetric with a functional form controlled by two variable parameters. The parameters are calculated using measurements of gas radiation at two wavelengths in the infrared spectrum. Infrared emission and absorption measurements at two or more wavelengths provide a method of determining a gas temperature profile along a path through the gas by using a radiation source and receiver located outside the gas stream being measured. This permits simplified spectral scanning of a jet or rocket engine exhaust stream with the instrumentation outside the exhaust gas stream. This program provides an iterative-cyclic computation in which an initial assumed temperature profile is altered in shape until the computed emission and absorption agree, within specified limits, with the actual instrument measurements of emission and absorption. Temperature determination by experimental measurements of emission and absorption at two or more wavelengths is also provided by this program. Additionally, the program provides a technique for selecting the wavelengths to be used for determining the temperature profiles prior to the beginning of the experiment. By using this program feature, the experimenter has a higher probability of selecting wavelengths which will result in accurate temperature profile measurements. This program provides the user with a technique for determining whether this program will be sufficiently accurate for his particular application, as well as providing a means of finding the solution. The input to the program consists of four types of data: (1) computer program control constants, (2) measurements of gas radiance and transmittance at selected wavelengths, (3) tabulations from the literature of gas

  7. A heated chamber burner for atomic absorption spectroscopy.

    PubMed

    Venghiattis, A A

    1968-07-01

    A new heated chamber burner is described. The burner is of the premixed type, and burner heads of the types conventionally used in atomic absorption may be readily adapted to it. This new sampling system has been tested for Ag, Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Si, Ti, and Zn in aqueous solutions. An improvement of the order of ten times has been obtained in sensitivity, and in detection limits as well, for the elements determined. Interferences controllable are somewhat more severe than in conventional burners but are controllable. PMID:20068792

  8. Ion irradiation of Allende meteorite probed by visible, IR, and Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Brunetto, R.; Lantz, C.; Ledu, D.; Baklouti, D.; Barucci, M. A.; Beck, P.; Delauche, L.; Dionnet, Z.; Dumas, P.; Duprat, J.; Engrand, C.; Jamme, F.; Oudayer, P.; Quirico, E.; Sandt, C.; Dartois, E.

    2014-07-01

    Little is known about carbonaceous asteroids weathering in space as previous studies have struggled to define a general spectral trend among dark surfaces. Here we present experiments on ion irradiation of the Allende meteorite, performed using 40 keV He+ and Ar+ ions, as a simulation of solar wind irradiation of primitive bodies surfaces. We used different fluences up to 3 × 1016 ions/cm2, corresponding to short timescales of ∼103-104 yrs in the main asteroid belt. Samples were analyzed before and after irradiation using visible to far-IR (0.4-50 μm) reflectance spectroscopy, and Raman micro-spectroscopy. Similarly to what observed in previous experiments, results show a reddening and darkening of VIS-NIR reflectance spectra. These spectral variations are however comparable to other spectral variations due to viewing geometry, grain size, and sample preparation, suggesting an explanation for the contradictory space weathering studies of dark asteroids. After irradiation, the infrared bands of the matrix olivine silicates change profile and shift to longer wavelength, possibly as a consequence of a more efficient sputtering effect on Mg than Fe (lighter and more volatile species are preferentially sputtered backwards) and/or preferential amorphization of Mg-rich olivine. Spectral variations are compatible with the Hapke weathering model. Raman spectroscopy shows that the carbonaceous component is substantially affected by irradiation: different degrees of de-ordering are produced as a function of dose, to finally end with a highly disordered carbon. All observed modifications seem to scale with the nuclear elastic dose.

  9. Simulation-based comparison of noise effects in wavelength modulation spectroscopy and direct absorption TDLAS

    NASA Astrophysics Data System (ADS)

    Lins, B.; Zinn, P.; Engelbrecht, R.; Schmauss, B.

    2010-08-01

    A simulative investigation of noise effects in wavelength modulation spectroscopy (WMS) and direct absorption diode laser absorption spectroscopy is presented. Special attention is paid to the impact of quantization noise of the analog-to-digital conversion (ADC) of the photodetector signal in the two detection schemes with the goal of estimating the necessary ADC resolution for each technique. With laser relative intensity noise (RIN), photodetector shot noise and thermal amplifier noise included, the strategies used for noise reduction in direct and wavelength modulation spectroscopy are compared by simulating two respective systems. Results show that because of the combined effects of dithering by RIN and signal averaging, the resolutions required for the direct absorption setup are only slightly higher than for the WMS setup. Only for small contributions of RIN an increase in resolution will significantly improve signal quality in the direct scheme.

  10. [Retrieval of tropospheric NO2 by multi axis differential optical absorption spectroscopy].

    PubMed

    Xu, Jin; Xie, Pin-hua; Si, Fu-qi; Dou, Ke; Li, Ang; Liu, Yu; Liu, Wen-qing

    2010-09-01

    A method of retrieving NO2 in troposphere based on multi axis differential optical absorption spectroscopy (MAX-DOAS) was introduced. The differential slant column density (dSCD) of NO2 was evaluated by differential optical absorption spectroscopy (DOAS), removing the Fraunhofer structure and Ring effect. Combining the results of different observing directions, the tropospheric NO2 differential slant column density (deltaSCD) was evaluated, and the air mass factor (AMF) was calculated with the radiative transfer model SCIATRAN and the tropospheric NO2 vertical column density (VCD) was retrieved. To ensure the accuracy of the results, it was compared with the results of long path differential optical absorption spectroscopy (LP-DOAS), a good accordance was shown with the correlation coefficients of 0.94027 and 0.96924. PMID:21105419

  11. NMR and IR Spectroscopy for the Structural Characterization of Edible Fats and Oils: An Instrumental Analysis Laboratory

    ERIC Educational Resources Information Center

    Crowther, Molly W.

    2008-01-01

    This article describes an upper-level instrumental laboratory for undergraduates that explores the complementary nature of IR and NMR spectroscopy for analysis of several edible fats and oils that are structurally similar but differ in physical properties and health implications. Five different fats and oils are analyzed for average chain length,…

  12. Detection and classification of salmonella serotypes using spectral signatures collected by fourier transform infrared (FT-IR) spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spectral signatures of Salmonella serotypes namely Salmonella Typhimurium, Salmonella Enteritidis, Salmonella Infantis, Salmonella Heidelberg and Salmonella Kentucky were collected using Fourier transform infrared spectroscopy (FT-IR). About 5-10 µL of Salmonella suspensions with concentrations of 1...

  13. HST/STIS results on circumstellar disks and jets, future coronography and technology for IR multi-object spectroscopy

    NASA Technical Reports Server (NTRS)

    Woodgate, Bruce E.

    2002-01-01

    Results of studies of circumstellar disks and jets obtained by HST/STIS visible coronagraphy and UV spectroscopy, and by ground-based Fabry-Perot coronagraphy will be presented. Future improvements in coronagraphy will be discussed. The development of microshutter arrays as programmable multi-object selectors for the NGST near IR spectrograph will be described.

  14. Spectroscopic (FT-IR, FT-Raman, UV absorption, 1H and 13C NMR) and theoretical (in B3LYP/6-311++G** level) studies on alkali metal salts of caffeic acid

    NASA Astrophysics Data System (ADS)

    Świsłocka, Renata

    The effect of some metals on the electronic system of benzoic and nicotinic acids has recently been investigated by IR, Raman and UV spectroscopy [1-3]. Benzoic and nicotinic acids are regarded model systems representing a wide group of aromatic ligands which are incorporated into enzymes. In this work the FT-IR (in solid state and in solution), FT-Raman, UV absorption and 1H and 13C NMR spectra of caffeic acid (3,4-dihydroxycinnamic acid) and its salts with lithium, sodium, potassium, rubidium and caesium were registered, assigned and analyzed. The effect of alkali metals on the electronic system of ligands was discussed. Studies of differences in the number and position of bands from the IR, Raman, UV absorption spectra and chemical shifts from NMR spectra allowed to conclude on the distribution of electronic charge in the molecules, the delocalization energy of π electrons and the reactivity of ligands in metal complexes. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G** basis set. Bond lengths, angles and dipole moments for the optimized structures of caffeic acid and lithium, sodium, potassium caffeinates were also calculated. The theoretical wavenumbers and intensities of IR spectra were obtained. The calculated parameters were compared to the experimental characteristics of investigated compounds. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris.

  15. Spectroscopic (FT-IR, FT-Raman, UV absorption, 1H and 13C NMR) and theoretical (in B3LYP/6-311++G** level) studies on alkali metal salts of caffeic acid.

    PubMed

    Świsłocka, Renata

    2013-01-01

    The effect of some metals on the electronic system of benzoic and nicotinic acids has recently been investigated by IR, Raman and UV spectroscopy [1-3]. Benzoic and nicotinic acids are regarded model systems representing a wide group of aromatic ligands which are incorporated into enzymes. In this work the FT-IR (in solid state and in solution), FT-Raman, UV absorption and (1)H and (13)C NMR spectra of caffeic acid (3,4-dihydroxycinnamic acid) and its salts with lithium, sodium, potassium, rubidium and caesium were registered, assigned and analyzed. The effect of alkali metals on the electronic system of ligands was discussed. Studies of differences in the number and position of bands from the IR, Raman, UV absorption spectra and chemical shifts from NMR spectra allowed to conclude on the distribution of electronic charge in the molecules, the delocalization energy of π electrons and the reactivity of ligands in metal complexes. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G** basis set. Bond lengths, angles and dipole moments for the optimized structures of caffeic acid and lithium, sodium, potassium caffeinates were also calculated. The theoretical wavenumbers and intensities of IR spectra were obtained. The calculated parameters were compared to the experimental characteristics of investigated compounds. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris. PMID:22369898

  16. Absorption spectroscopy in the ultraviolet and visible spectral range of hexavalent chromium aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mignani, Anna G.; Spadoni, Lorenzo

    1999-09-01

    In order to demonstrate the possibility of performing direct absorption spectroscopy of Hexavalent Chromium aqueous solutions, absorption measurements were performed at the dual- beam spectrophotometer in the 250 - 850 nm spectral range, with 10 mm and 100 mm path lengths. Low concentration (26 - 520 (mu) g/l) (and high concentration (2.6 - 52 mg/l) solutions were analyzed, showing that it is possible to implement a basic instrumentation for risk condition monitoring and a more advanced instrumentation for quantitative measurements.

  17. Time- and frequency-resolved coherent two-dimensional IR spectroscopy: Its complementary relationship with the coherent two-dimensional Raman scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Kisam; Cho, Minhaeng

    1998-12-01

    A theoretical description of the coherent two-dimensional IR spectroscopy is presented. Two consecutive IR pulses can be used to create two consecutive vibrational coherence states. The third off-resonant optical pulse is used to probe the two-dimensional transient grating thus created and then the scattered field is measured. The corresponding nonlinear response functions are obtained in the analytic forms by assuming that the vibrational modes are weakly anharmonic Brownian oscillators. Since one can experimentally control the two delay times as well as the two IR field frequencies, it is possible to extract vital information on the vibrational relaxation in time domain as well as the intra- and intermolecular vibrational mode couplings in frequency domain. Numerical calculations are carried out to clarify the quantitative features of the coherent 2D IR spectroscopic phenomenon.

  18. Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

    NASA Technical Reports Server (NTRS)

    Lopez, Gabriel P.; Niemczyk, Thomas

    1999-01-01

    Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone

  19. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1976-01-01

    Laser-based spectrophotometric methods which have been proposed for the detection of trace concentrations of gaseous contaminants include Raman backscattering (LIDAR) and passive radiometry (LOPAIR). Remote sensing techniques using laser spectrometry are presented and in particular a simple long-path laser absorption method (LOLA), which is capable of resolving complex mixtures of closely related trace contaminants at ppm levels is discussed. A number of species were selected for study which are representative of those most likely to accumulate in closed environments, such as submarines or long-duration manned space flights. Computer programs were developed which will permit a real-time analysis of the monitored atmosphere. Estimates of the dynamic range of this monitoring technique for various system configurations, and comparison with other methods of analysis, are given.

  20. Total absorption spectroscopy of N = 51 nucleus 85Se

    NASA Astrophysics Data System (ADS)

    Goetz, K. C.; Grzywacz, R. K.; Rykaczewski, K. P.; Karny, M.; Fialkowska, A.; Wolinska-Cichocka, M.; Rasco, B. C.; Zganjar, E. F.; Johnson, J. W.; Gross, C. J.

    2014-09-01

    An experimental campaign utilizing the Modular Total Absorption Spectrometer (MTAS) was conducted at the HRIBF facility in January of 2012. The campaign studied 22 isotopes, many of which were identified as the highest priority for decay heat analysis during a nuclear fuel cycle, see the report by the OECD-IAEA Nuclear Energy Agency in 2007. The case of 85Se will be discussed. 85Se is a Z = 34, N = 51 nucleus with the valence neutron located in the positive parity sd single particle state. Therefore, its decay properties are determined by interplay between first forbidden decays of the valence neutron and Gamow-Teller decay of a 78Ni core. Analysis of the data obtained during the January 2012 run indicates a significant increase of the beta strength function when compared with previous measurements, see Ref..

  1. Characterization of Paracoccidioides brasiliensis by FT-IR spectroscopy and nanotechnology.

    PubMed

    Ferreira, Isabelle; Ferreira-Strixino, Juliana; Castilho, Maiara L; Campos, Claudia B L; Tellez, Claudio; Raniero, Leandro

    2016-01-01

    Paracoccidioides brasiliensis, the etiological agent of paracoccidioidomycosis, is a dimorphic fungus existing as mycelia in the environment (or at 25°C in vitro) and as yeast cells in the human host (or at 37°C in vitro). Because mycological examination of lesions in patients frequently is unable to show the presence of the fungus and serological tests can misdiagnose the disease with other mycosis, the development of new approach's for molecular identification of P. brasiliensis spurges is needed. This study describes the use of a gold nanoprobe of a known gene sequence of P. brasiliensis as a molecular tool to identify P. brasiliensis by regular polymerase chain reaction (PCR) associated with a colorimetric methods. This approach is suitable for testing in remote areas because it does not require any further step than gene amplification, being safer and cheaper than electrophoresis methods. The proposed test showed a color change of the PCR reaction mixture from red to blue in negative samples, whereas the solution remains red in positive samples. We also performed a Fourier Transform Infrared (FT-IR) Spectroscopy analysis to characterize and compare the chemical composition between yeast and mycelia forms, which revealed biochemical differences between these two forms. The analysis of the spectra showed that differences were distributed in chemical bonds of proteins, lipids and carbohydrates. The most prominent difference between both forms was vibration modes related to 1,3-β-glucan usually found in mycelia and 1,3-α-glucan found in yeasts and also chitin forms. In this work, we introduce FT-IR as a new method suitable to reveal overall differences that biochemically distinguish each form of P. brasiliensis that could be additionally used to discriminate biochemical differences among a single form under distinct environmental conditions. PMID:26241825

  2. Correlated IR spectroscopy and visible light scattering measurements of mineral dust aerosol

    NASA Astrophysics Data System (ADS)

    Meland, B.; Kleiber, P. D.; Grassian, V. H.; Young, M. A.

    2010-10-01

    A combined infrared spectroscopy and visible light scattering study of the optical properties of quartz aerosol, a major component of atmospheric dust, is reported. Scattering phase function and polarization measurements for quartz dust at three visible wavelengths (470, 550, 660 nm) are compared with results from T-matrix theory simulations using a uniform spheroid model for particle shape. Aerosol size distributions were measured simultaneously with light scattering. Particle shape distributions were determined in two ways: (1) analysis of electron microscope images of the dust, and (2) spectral fitting of infrared resonance extinction features. Since the aerosol size and shape distributions were measured, experimental scattering data could be directly compared with T-matrix simulations with no adjustable parameters. χ2 analysis suggests that T-matrix simulations based on a uniform spheroid approximation can be used to model the optical properties of irregularly shaped dust particles in the accumulation mode size range, provided the particle shape distribution can be reliably determined. Particle shape distributions derived from electron microscope image analysis give poor fits, indicating that two-dimensional images may not give an accurate representation of the shape distribution for three-dimensional particles. However, simulations based on particle shape models inferred from IR spectral analysis give excellent fits to the experimental data. Our work suggests that correlated IR spectral and visible light scattering measurements, together with the use of theoretical light scattering models, may offer a more accurate method for characterizing atmospheric dust loading, and aerosol composition, size, and shape distributions, which are of great importance in climate modeling.

  3. Characterization of Paracoccidioides brasiliensis by FT-IR spectroscopy and nanotechnology

    NASA Astrophysics Data System (ADS)

    Ferreira, Isabelle; Ferreira-Strixino, Juliana; Castilho, Maiara L.; Campos, Claudia B. L.; Tellez, Claudio; Raniero, Leandro

    2016-01-01

    Paracoccidioides brasiliensis, the etiological agent of paracoccidioidomycosis, is a dimorphic fungus existing as mycelia in the environment (or at 25 °C in vitro) and as yeast cells in the human host (or at 37 °C in vitro). Because mycological examination of lesions in patients frequently is unable to show the presence of the fungus and serological tests can misdiagnose the disease with other mycosis, the development of new approach's for molecular identification of P. brasiliensis spurges is needed. This study describes the use of a gold nanoprobe of a known gene sequence of P. brasiliensis as a molecular tool to identify P. brasiliensis by regular polymerase chain reaction (PCR) associated with a colorimetric methods. This approach is suitable for testing in remote areas because it does not require any further step than gene amplification, being safer and cheaper than electrophoresis methods. The proposed test showed a color change of the PCR reaction mixture from red to blue in negative samples, whereas the solution remains red in positive samples. We also performed a Fourier Transform Infrared (FT-IR) Spectroscopy analysis to characterize and compare the chemical composition between yeast and mycelia forms, which revealed biochemical differences between these two forms. The analysis of the spectra showed that differences were distributed in chemical bonds of proteins, lipids and carbohydrates. The most prominent difference between both forms was vibration modes related to 1,3-β-glucan usually found in mycelia and 1,3-α-glucan found in yeasts and also chitin forms. In this work, we introduce FT-IR as a new method suitable to reveal overall differences that biochemically distinguish each form of P. brasiliensis that could be additionally used to discriminate biochemical differences among a single form under distinct environmental conditions.

  4. High-pressure study of ScH3: Raman, infrared, and visible absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kume, Tetsuji; Ohura, Hiroyuki; Takeichi, Tomoo; Ohmura, Ayako; Machida, Akihiko; Watanuki, Tetsu; Aoki, Katsutoshi; Sasaki, Shigeo; Shimizu, Hiroyasu; Takemura, Kenichi

    2011-08-01

    Raman, IR, and visible absorption spectra of scandium trihydride (ScH3) have been measured at high pressures up to 50 GPa, to investigate the structural and electronic phase transitions. Successive hcp-intermediate-fcc phase transitions were observed at 25 and 46 GPa by Raman and IR measurements. It was suggested that the intermediate phase of ScH3 takes the same structure as that of YH3 with a long periodicity of the stacking of the metal planes. The visible absorption spectra allowed us to determine that the energy gap of ScH3 is 1.7 eV at the ambient condition and is closed around 50 GPa, at which the crystal structure transforms to fcc.

  5. Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates

    PubMed Central

    Behm, R Jürgen

    2014-01-01

    Summary As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed. PMID:24991512

  6. Grism Performance for Mid-IR (5-40 microns) Spectroscopy

    NASA Technical Reports Server (NTRS)

    Ennico, K. A.; Mar, D. J.; Jaffe, D. T.; Marsh, J. P.; Keller, L. D.; Herter, T. L.; Greene, T. P.; Adams, J. D.

    2006-01-01

    Grisms provide a straightforward method to transform an imager into a spectrometer with little change to the original imaging optics. This paper addresses the performance of a suite of grisms as part of an Astrobiology Science and Instrument Development (ASTID) Program to implement a moderate resolution spectroscopic capability to the mid/far-IR facility instrument FORCAST for the Stratospheric Observatory For Infrared Astronomy (SOFIA) [see accompanying abstract by Adams et al.]. A moderate resolution mid-IR spectrometer on SOFIA will offer advantages not available to either ground or space-based instruments after the Spitzer Space Telescope ceases operation in approx. 2007. SOFIA will begin operations in 2007 and will have an operational lifetime of approx. 20 years. From aircraft altitudes, it will be possible to cover a range of wavelengths, particularly in the critical 5-9 micron band, where detection of astrobiologically interesting molecules have key spectral signatures, that are not accessible from the ground. This grism suite consists of six grisms: four monolithic Si grisms [see accompanying abstract by Mar et al.] and two KRS-5 grisms. These devices will allow long slit low-resolution and short slit, cross-dispersed high-resolution spectroscopic modes selectable by simply moving the camera filter wheels. This configuration will enable observing programs to gather images and spectra in a single SOFIA flight. The four silicon grisms, whose performance is highlighted in this paper, will operate in the following wavelength ranges: 5-8, 17-28, and 28-37 microns. In the 5-8 micron range, R=1200 is achievable for a 2 arcsecond slit using the grism as a cross-disperser. For the 17-28 and 28-37 micron ranges, the resolving powers are R approx. 130, 250 when used in low orders with a slit of 3 arcseconds. The silicon grisms demonstrate a new family of dispersive elements with good optical performance for spectroscopy from 1.2-8 micron and beyond 18 microns

  7. Complementarity of UV and IR differential absorption lidar for global measurements of atmospheric species

    NASA Technical Reports Server (NTRS)

    Megie, G.; Menzies, R. T.

    1980-01-01

    An analysis of the potential capabilities of a spectrally diversified DIAL technique for monitoring atmospheric species is presented assuming operation from an earth-orbiting platform. Emphasis is given to the measurement accuracies and spatial and temporal resolutions required to meet present atmospheric science objectives. The discussion points out advantages of spectral diversity to perform comprehensive studies of the atmosphere; in general it is shown that IR systems have an advantage in lower atmospheric measurements, while UV systems are superior for middle and upper atmospheric measurements.

  8. Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

    SciTech Connect

    Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N.; Liliental-Weber, Z.

    2006-09-25

    X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.

  9. Absorption spectroscopy of powdered materials using time-resolved diffuse optical methods.

    PubMed

    D'Andrea, Cosimo; Obraztsova, Ekaterina A; Farina, Andrea; Taroni, Paola; Lanzani, Guglielmo; Pifferi, Antonio

    2012-11-10

    In this paper a novel method, based on time-resolved diffuse optical spectroscopy, is proposed to measure the absorption of small amounts of nanostructured powder materials independent of scattering. Experimental validation, in the visible and near-infrared spectral range, has been carried out on India Inkparticles. The effectiveness of the technique to measure scattering-free absorption is demonstrated on carbon nanotubes. The comparison between the absorption spectra acquired by the proposed method and conventional measurements performed with a commercial spectrophotometer is discussed. PMID:23142900

  10. Difference Between Far-Infrared Photoconductivity Spectroscopy and Absorption Spectroscopy: Theoretical Evidence of the Electron Reservoir Mechanism

    NASA Astrophysics Data System (ADS)

    Toyoda, Tadashi; Fujita, Maho; Uchida, Tomohisa; Hiraiwa, Nobuyoshi; Fukuda, Taturo; Koizumi, Hideki; Zhang, Chao

    2013-08-01

    The intriguing difference between far-infrared photoconductivity spectroscopy and absorption spectroscopy in the measurement of the magnetoplasmon frequency in GaAs quantum wells reported by Holland et al. [Phys. Rev. Lett. 93, 186804 (2004)] remains unexplained to date. This Letter provides a consistent mechanism to solve this puzzle. The mechanism is based on the electron reservoir model for the integer quantum Hall effect in graphene [Phys. Lett. A 376, 616 (2012)]. We predict sharp kinks to appear in the magnetic induction dependence of the magnetoplasmon frequency at very low temperatures such as 14 mK in the same GaAs quantum well sample used by Holland et al..

  11. The Synthesis and Characterization of a Group of Transition Metal Octabutoxynaphthalocyanines and the Absorption and Emission Properties of the Co, Rh, Ir, Ni, Pd and Pt Members of This Group

    PubMed Central

    Kim, Junhwan; Soldatova, Alexandra V.; Rodgers, Michael A. J.; Kenney, Malcolm E.

    2013-01-01

    The synthesis and photophysical properties of new metallo-octabutoxynaphthalocyanines with Rh(III), Ir(III), and Pt(II) are reported. Various metals were inserted into the metal-free octabutoxynaphthalocyanine and the resultant metal complexes were fully characterized by NMR, UV-vis spectroscopy, and mass spectrometry. The absorption and emission properties of these new complexes were also examined and compared to those of Co(II), Ni(II), and Pd(II) octabutoxynaphthalocyanines. The results provide useful information to understand the effect of these transition metals on the properties of this macrocyclic ring. PMID:23745014

  12. Quartz crystal microbalance and infrared reflection absorption spectroscopy characterization of bisphenol A absorption in the poly(acrylate) thin films.

    PubMed

    Li, Guifeng; Morita, Shigeaki; Ye, Shen; Tanaka, Masaru; Osawa, Masatoshi

    2004-02-01

    The absorption process of bisphenol A (BPA) in a number of poly(acrylate) thin films, such as poly(2-methoxyethyl acrylate) (PMEA), poly(ethyl acrylate) (PEA), poly(n-butyl methacrylate) (PBMA), and poly(methyl methacrylate) (PMMA), has been investigated by quartz crystal microbalance (QCM) and infrared reflection absorption spectroscopy (IRRAS) measurements. Both QCM and IRRAS measurements show that the BPA molecules absorb in PMEA, PEA, and PBMA thin films but not in PMMA thin film. The differences in the BPA absorption behavior are mainly attributed to the difference in the glass transition temperature (T(g)) between these polymers. This absorption behavior also depends on the BPA concentration and polymer film thickness. Furthermore, IRRAS characterization demonstrates that the hydrogen bonding is formed between the hydroxyl group in BPA and the carbonyl group in the poly(acrylate) thin films. BPA molecule absorbed in these polymer thin films can be removed by ethanol rinse treatment. By optimizing experimental conditions for the QCM electrode modified by PMEA thin film, detection limitation of approximately 1 ppb for BPA can be realized by the in situ QCM measurement. This method is expected to be a sensitive in situ detection way for trace BPA in the environmental study. PMID:14750877

  13. Design of mini-multi-gas monitoring system based on IR absorption

    NASA Astrophysics Data System (ADS)

    Tan, Qiu-lin; Zhang, Wen-dong; Xue, Chen-yang; Xiong, Ji-jun; Ma, You-chun; Wen, Fen

    2008-07-01

    In this paper, a novel non-dispersive infrared ray (IR) gas detection system is described. Conventional devices typically include several primary components: a broadband source (usually an incandescent filament), a rotating chopper shutter, a narrow-band filter, a sample tube and a detector. But we mainly use the mini-multi-channel detector, electrical modulation means and mini-gas-cell structure. To solve the problems of gas accidents in coal mines, and for family safety that results from using gas, this new IR detection system with integration, miniaturization and non-moving parts has been developed. It is based on the principle that certain gases absorb infrared radiation at specific (and often unique) wavelengths. The infrared detection optics principle used in developing this system is mainly analyzed. The idea of multi-gas detection is introduced and guided through the analysis of the single-gas detection. Through researching the design of cell structure, a cell with integration and miniaturization has been devised. By taking a single-chip microcomputer (SCM) as intelligence handling, the functional block diagram of a gas detection system is designed with the analyzing and devising of its hardware and software system. The way of data transmission on a controller area network (CAN) bus and wireless data transmission mode is explained. This system has reached the technology requirement of lower power consumption, mini-volume, wide measure range, and is able to realize multi-gas detection.

  14. Laboratory atomic transition data for precise optical quasar absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Murphy, Michael T.; Berengut, Julian C.

    2014-02-01

    Quasar spectra reveal a rich array of important astrophysical information about galaxies which intersect the quasar line of sight. They also enable tests of the variability of fundamental constants over cosmological time- and distance-scales. Key to these endeavours are the laboratory frequencies, isotopic and hyperfine structures of various metal-ion transitions. Here, we review and synthesize the existing information about these quantities for 43 transitions which are important for measuring possible changes in the fine-structure constant, α, using optical quasar spectra, i.e. those of Na, Mg, Al, Si, Ca, Cr, Mn, Fe, Ni and Zn. We also summarize the information currently missing that precludes more transitions being used. We present an up-to-date set of coefficients, q, which define the sensitivity of these transitions to variations in α. New calculations of isotopic structures and q-coefficients are performed for Si II and Ti II, including Si II λ1808 and Ti IIλλ1910.6/1910.9 for the first time. Finally, simulated absorption-line spectra are used to illustrate the systematic errors expected if the isotopic/hyperfine structures are omitted from profile fitting analyses. To ensure transparency, repeatability and currency of the data and calculations, we supply a comprehensive data base as Supporting Information. This will be updated as new measurements and calculations are performed.

  15. The Role of Polycyclic Aromatic Hydrocarbons in Dense Cloud Absorption Features: The Last Major Unanswered Question in Interstellar Ice Spectroscopy

    NASA Astrophysics Data System (ADS)

    Chiar, Jean

    Interstellar dust plays a vital role in the star formation process and the eventual formation of planetary systems including our own. Ice mantles are an important component of the dust: reactions involving simple ices can create more complex (and astrobiologically interesting) molecules, and ices sublimated back into the gas phase influence the gas- phase chemistry. Although polycyclic aromatic hydrocarbons (PAHs) are commonly thought to be very abundant interstellar species and, as such, are likely to be important components of interstellar ices, their contribution to the infrared spectra and chemistry of ices in dense molecular clouds is an open question. This program makes extensive use of three major NASA-funded databases: the Spitzer archive, the 2MASS archive, and the NASA Ames PAH database in order to answer the last major unanswered question in interstellar ice spectroscopy: what role do PAHs play in contributing to unidentified absorption features observed in dense cloud spectra. PAHs are observed to be present and abundant in nearly all phases of the galactic and extragalactic interstellar medium. The evidence for the ubiquity of interstellar PAHs is the widespread well-known family of prominent emission bands at 3.28, 6.2, 7.7, 8.6, and 11.2 micron. To date, these PAH bands have been most easily detected in regions where individual gas phase PAH molecules (neutrals and ions) become highly vibrationally excited by the ambient radiation field. While PAHs and closely related aromatic materials should be present throughout dense interstellar regions, PAH emission is quenched in cold dark dense clouds. Also, in these regions, most PAHs should efficiently condense out onto dust grains, either as "pure" solids or as "guest molecules" in icy grain mantles, much as is the case for most other interstellar molecules. Thus, in dense molecular clouds, condensed PAHs will give rise to IR absorption bands rather than emission features. While PAH absorption has been

  16. WaFIRS, a Waveguide Far-IR Spectrometer: Enabling Space-Borne Spectroscopy of High-z Galaxies in the Far-IR and Submm

    NASA Technical Reports Server (NTRS)

    Bradford, C. M.; Bock, J. J.; Dragovan, M.; Earle, L.; Glenn, J.; Naylor, B.; Nguyen, H.; Zmuidzinas, J.

    2004-01-01

    The discovery of galaxies beyond z approximately equal to 1 which emit the bulk of their luminosity at long wavelengths has demonstrated the need for high sensitivity, broadband spectroscopy in the far-IR/submm/mm bands. Because many of these sources are not detectable in the optical, long wavelength spectroscopy is key to measuring their redshifts and ISM conditions. The continuum source list will increase in the next decade with new ground-based instruments (SCUBA2, Bolocam, MAMBO) and the surveys of HSO and SIRTF. Yet the planned spectroscopic capabilities lag behind, primarily due to the difficulty in scaling existing IR spectrograph designs to longer wavelengths. To overcome these limitations, we are developing WaFIRS, a novel concept for long-wavelength spectroscopy which utilizes a parallel-plate waveguide and a curved diffraction grating. WaFIRS provides the large (approximately 60%) instantaneous bandwidth and high throughput of a conventional grating system, but offers a dramatic reduction in volume and mass. WaFIRS requires no space overheads for extra optical elements beyond the diffraction grating itself, and is two-dimensional because the propagation is confined between two parallel plates. Thus several modules could be stacked to multiplex either spatially or in different frequency bands. The size and mass savings provide opportunities for spectroscopy from space-borne observatories which would be impractical with conventional spectrographs. With background-limited detectors and a cooled 3.5 telescope, the line sensitivity would be better than that of ALMA, with instantaneous broad-band coverage. We have built and tested a WaFIRS prototype for 1-1.6 mm, and are currently constructing Z-Spec, a 100 mK model to be used as a ground-based lambda/DELTAlambda approximately equal to 350 submillimeter galaxy redshift machine.

  17. Forensic Hair Differentiation Using Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectroscopy.

    PubMed

    Manheim, Jeremy; Doty, Kyle C; McLaughlin, Gregory; Lednev, Igor K

    2016-07-01

    Hair and fibers are common forms of trace evidence found at crime scenes. The current methodology of microscopic examination of potential hair evidence is absent of statistical measures of performance, and examiner results for identification can be subjective. Here, attenuated total reflection (ATR) Fourier transform-infrared (FT-IR) spectroscopy was used to analyze synthetic fibers and natural hairs of human, cat, and dog origin. Chemometric analysis was used to differentiate hair spectra from the three different species, and to predict unknown hairs to their proper species class, with a high degree of certainty. A species-specific partial least squares discriminant analysis (PLSDA) model was constructed to discriminate human hair from cat and dog hairs. This model was successful in distinguishing between the three classes and, more importantly, all human samples were correctly predicted as human. An external validation resulted in zero false positive and false negative assignments for the human class. From a forensic perspective, this technique would be complementary to microscopic hair examination, and in no way replace it. As such, this methodology is able to provide a statistical measure of confidence to the identification of a sample of human, cat, and dog hair, which was called for in the 2009 National Academy of Sciences report. More importantly, this approach is non-destructive, rapid, can provide reliable results, and requires no sample preparation, making it of ample importance to the field of forensic science. PMID:27412186

  18. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy

    SciTech Connect

    Stamm, A.; Schwing, K.; Gerhards, M.

    2014-11-21

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S{sub 0}) and cationic (D{sub 0}) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC){sub 2} as well as its mono- and dihydrate (7H4MC){sub 2}(H{sub 2}O){sub 1-2} are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction.

  19. XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

    NASA Technical Reports Server (NTRS)

    Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

    2006-01-01

    The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

  20. Quantitative monitoring of membrane permeation via in-situ ATR FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan; Miller, Daniel

    Ion conducting membranes are of interest for various energy applications including fuel cells and artificial photosynthesis systems. Within the context of artificial photosynthesis, membranes are desired that facilitate the ion transport necessary to feed the electrochemical reactions while meeting various additional selectivity and permeability demands depending on the CO2 reduction products. Herein, we demonstrate the use of in-situ ATR FT-IR spectroscopy to quantitatively resolve the concentration of single and multicomponent mixtures of various CO2 reduction products including methanol, formate and acetate. We then apply this methodology to the in-situ monitoring of the permeation of single and multicomponent mixtures across commercially available membranes. Membrane permeabilities and selectivities calculated from the single component time-resolved concentration curves are compared to the multicomponent permeation experiments. This material is based upon work performed at the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC000493.

  1. Diagnostics of cancer tissues by fiber optic evanescent wave Fourier transform IR (FEW-FTIR) spectroscopy

    NASA Astrophysics Data System (ADS)

    Afanasyeva, Natalia I.; Kolyakov, Sergei F.; Letokhov, Vladilen S.; Golovkina, Viktoriya N.

    1997-08-01

    Fiber optic evanescent wave Fourier transform infrared (FEW- FTIR) spectroscopy using fiberoptic sensors operated in the attenuated total reflection (ATR) regime in the middle infrared (IR) region of the spectrum (850 - 1850 cm-1) has recently found application in the diagnostics of tissues. The method is suitable for noninvasive and rapid (seconds) direct measurements of the spectra of normal and pathological tissues in vitro, ex vivo and in vivo. The aim of our studies is the express testing of various tumor tissues at the early stages of their development. The method is expected to be further developed for endoscopic and biopsy applications. We measured in vivo the skin normal and malignant tissues on surface (directly on patients) in various cases of basaloma, melanoma and nevus. The experiments were performed in operating room for measurements of skin in the depth (under/in the layers of epidermis), human breast, stomach, lung, kidney tissues. The breast and skin tissues at different stages of tumor or cancer were distinguished very clearly in spectra of amide, side cyclic and noncyclic hydrogen bonded fragments of aminoacid residuals, phosphate groups and sugars. Computer monitoring is being developed for diagnostics.

  2. Molecular IR Spectroscopy: New Trends and Methods of Noninvasive Diagnostics of Tissue IN VIVO

    NASA Astrophysics Data System (ADS)

    Afanasyeva, Natalia; Bruch, Reinhard

    1998-05-01

    Fiberoptic evanescent wave Fourier transform infrared (FEW-FTIR) spectroscopy using fiberoptic sensors operated in the attenuated total reflection (ATR) regime in the middle infrared (IR) region of the spectrum (850-1850 cm-1) has recently been applied to the diagnostics of tissues. The method is suitable for noninvasive and rapid (seconds) direct measurements of the spectra of normal and pathological tissues in vitro, ex vivo and in vivo. The aim of our studies is the express testing of various tumor tissues at the early stages of their development. The method is expected to be further developed for endoscopic and biopsy applications. We measured the normal skin and malignant tissues in vivo on the surface (directly on patients) in various cases of basaloma, melanoma and nevus. The experiments were performed in the operating room to measure the skin in the depth (under/in the layers of epidermis) of human breast, stomach, lung, and kidney tissues. The breast and skin tissues at different stages of tumor or cancer were distinguished very clearly in spectra of amide, side cyclic and noncyclic hydrogen bonded fragments of aminoacid residuals, phosphate groups and sugars. Computer monitoring is being developed for diagnostics.

  3. IR spectroscopy of monohydrated tryptamine cation: Rearrangement of the intermolecular hydrogen bond induced by photoionization

    NASA Astrophysics Data System (ADS)

    Sakota, Kenji; Kouno, Yuuki; Harada, Satoshi; Miyazaki, Mitsuhiko; Fujii, Masaaki; Sekiya, Hiroshi

    2012-12-01

    Rearrangement of intermolecular hydrogen bond in a monohydrated tryptamine cation, [TRA(H2O)1]+, has been investigated in the gas phase by IR spectroscopy and quantum chemical calculations. In the S0 state of TRA(H2O)1, a water molecule is hydrogen-bonded to the N atom of the amino group of a flexible ethylamine side chain [T. S. Zwier, J. Phys. Chem. A 105, 8827 (2001), 10.1021/jp011659+]. A remarkable change in the hydrogen-bonding motif of [TRA(H2O)]+ occurs upon photoionization. In the D0 state of [TRA(H2O)1]+, the water molecule is hydrogen-bonded to the NH group of the indole ring of TRA+, indicating that the water molecule transfers from the amino group to NH group. Quantum chemical calculations are performed to investigate the pathway of the water transfer. Two potential energy barriers emerge in [TRA(H2O)1]+ along the intrinsic reaction coordinate of the water transfer. The water transfer event observed in [TRA(H2O)1]+ is not an elementary but a complex process.

  4. Identification of Forged Bank of England 20 Gbp Banknotes Using IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sonnex, Emily

    2014-06-01

    Bank of England notes of 20 GBP denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. A principal aim of this work was to develop a method so that a small, compact ATR FTIR instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 wn from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine 20 GBP notes were observed in the ν(OH) (ca. 3500 wn), ν(C-H) (ca. 2900 wn) and ν(C=O) (ca. 1750 wn) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper. Further to this, with an announcement by the Bank of England to produce polymer banknotes in the future, the work has been extended using Australian polymer banknotes to show that the method would be transferable.

  5. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy.

    PubMed

    Stamm, A; Schwing, K; Gerhards, M

    2014-11-21

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S0) and cationic (D0) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC)2 as well as its mono- and dihydrate (7H4MC)2(H2O)1-2 are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction. PMID:25416888

  6. IR near-field spectroscopy and imaging of single Li(x)FePO4 microcrystals.

    PubMed

    Lucas, I T; McLeod, A S; Syzdek, J S; Middlemiss, D S; Grey, C P; Basov, D N; Kostecki, R

    2015-01-14

    This study demonstrates the unique capability of infrared near-field nanoscopy combined with Fourier transform infrared spectroscopy to map phase distributions in microcrystals of Li(x)FePO4, a positive electrode material for Li-ion batteries. Ex situ nanoscale IR imaging provides direct evidence for the coexistence of LiFePO4 and FePO4 phases in partially delithiated single-crystal microparticles. A quantitative three-dimensional tomographic reconstruction of the phase distribution within a single microcrystal provides new insights into the phase transformation and/or relaxation mechanism, revealing a FePO4 shell surrounding a diamond-shaped LiFePO4 inner core, gradually shrinking in size and vanishing upon delithiation of the crystal. The observed phase propagation pattern supports recent functional models of LiFePO4 operation relating electrochemical performance to material design. This work demonstrates the remarkable potential of near-field optical techniques for the characterization of electrochemical materials and interfaces. PMID:25375874

  7. Investigation of calcium aluminates by IR spectroscopy in diffusely scattered light

    SciTech Connect

    Medin, A.S.; Borovkov, V.Yu.; Nissenbaum, V.D.; Yakerson, V.I.; Kazanskii, V.B.

    1989-01-01

    The hydroxyl covering and the adsorption sites for CO and H/sub 2/O on aluminum-calcium catalysts and supports with developed surfaces have been studied by IR spectroscopy in diffusely scattered light. The presence of several types of surface OH groups, viz., terminal groups bonded to calcium ions with different types of coordination, bridging OH groups, and groups appearing in (CaOH)/sup +/ groupings, which perform the role of compensating cations in the zeolite-like structure of calcium aluminates, has been established. The shifts of the bands of the OH groups upon the adsorption of C/sub 6/H/sub 6/ and cyclo-C/sub 6/H/sub 12/ point out their weakly acidic or basic character. When calcium aluminates are dehydroxylated, aprotic sites appear on their surfaces, and the rehydration of such surfaces is accompanied by the formation of OH groups and the weakening of the Al-O-M bonds (M = Al, Ca) with the appearance of additional sites for the strong adsorption of water.

  8. LISA: the Italian CRG beamline for x-ray Absorption Spectroscopy at ESRF

    NASA Astrophysics Data System (ADS)

    d'Acapito, F.; Trapananti, A.; Puri, A.

    2016-05-01

    LISA is the acronym of Linea Italiana per la Spettroscopia di Assorbimento di raggi X (Italian beamline for X-ray Absorption Spectroscopy) and is the upgrade of the former GILDA beamline installed on the BM08 bending magnet port of European Synchrotron Radiation Facility (ESRF). Within this contribution a full description of the project is provided.

  9. Application of x-ray absorption spectroscopy to the study of corrosion and inhibition

    SciTech Connect

    Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    X-ray absorption spectroscopy is a powerful technique for determination of valency and coordination. Measurements can be made in air or in situ under electrochemical control. The technique will be described and its application to the analysis of passive oxide films, corrosion products, and inhibitors will be reviewed.

  10. Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

    ERIC Educational Resources Information Center

    Weidenhammer, Jeffrey D.

    2007-01-01

    A circuit board analysis of the atomic absorption spectroscopy, which is used to measure lead content in a course for nonscience majors, is being presented. The experiment can also be used to explain the potential environmental hazards of unsafe disposal of various used electronic equipments.

  11. DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

    EPA Science Inventory

    A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers s...

  12. Absorption and Scattering Coefficients: A Biophysical-Chemistry Experiment Using Reflectance Spectroscopy

    ERIC Educational Resources Information Center

    Cordon, Gabriela B.; Lagorio, M. Gabriela

    2007-01-01

    A biophysical-chemistry experiment, based on the reflectance spectroscopy for calculating the absorption and scattering coefficients of leaves is described. The results show that different plants species exhibit different values for both the coefficients because of their different pigment composition.

  13. Gas concentration measurement by optical similitude absorption spectroscopy: methodology and experimental demonstration.

    PubMed

    Anselmo, Christophe; Welschinger, Jean-Yves; Cariou, Jean-Pierre; Miffre, Alain; Rairoux, Patrick

    2016-06-13

    We propose a new methodology to measure gas concentration by light-absorption spectroscopy when the light source spectrum is larger than the spectral width of one or several molecular gas absorption lines. We named it optical similitude absorption spectroscopy (OSAS), as the gas concentration is derived from a similitude between the light source and the target gas spectra. The main OSAS-novelty lies in the development of a robust inversion methodology, based on the Newton-Raphson algorithm, which allows retrieving the target gas concentration from spectrally-integrated differential light-absorption measurements. As a proof, OSAS is applied in laboratory to the 2ν3 methane absorption band at 1.66 µm with uncertainties revealed by the Allan variance. OSAS has also been applied to non-dispersive infra-red and the optical correlation spectroscopy arrangements. This all-optics gas concentration retrieval does not require the use of a gas calibration cell and opens new tracks to atmospheric gas pollution and greenhouse gases sources monitoring. PMID:27410280

  14. Characteristics of the complexing of chitosan with sodium dodecyl sulfate, according to IR spectroscopy data and quantum-chemical calculations

    NASA Astrophysics Data System (ADS)

    Shilova, S. V.; Romanova, K. A.; Galyametdinov, Yu. G.; Tret'yakova, A. Ya.; Barabanov, V. P.

    2016-06-01

    The complexing of protonated chitosan with dodecyl sulfate ions in water solutions is studied using IR spectroscopy data and quantum-chemical calculations. It is established that the electrostatic interaction between the protonated amino groups of chitosan and dodecyl sulfate ions is apparent in the IR spectrum as a band at 833 cm-1. The need to consider the effect the solvent has on the formation of hydrogen-bound ion pairs [CTS+ ṡ C12H25O 3 - ] is shown via a quantum-chemical simulation of the equilibrium geometry and the energy characteristics of complexing and hydration.

  15. Identification of multiple conformers of the ionic liquid [emim][tf2n] in the gas phase using IR/UV action spectroscopy.

    PubMed

    Booth, Ryan S; Annesley, Christopher J; Young, Justin W; Vogelhuber, Kristen M; Boatz, Jerry A; Stearns, Jaime A

    2016-06-22

    In this study we investigate the effect of deuteration and molecular beam temperature on the hydrogen bond in the ionic liquid [emim][tf2n]. Using IR/UV double resonance spectroscopy, we probe the microscopic structure of the [emim][tf2n] ion pair and its mono-deuterated, [emim-d1][tf2n], analog. Comparisons of the infrared absorption frequencies between these two species show that there are multiple conformers of the ion pair present in the gas phase and trapped through the molecular beam cooling process. Furthermore, each conformer has a characteristic red shift in the frequency of its C2-H group that reveals the variation in strength of a hydrogen bond between the cation and anion. PMID:27298098

  16. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    SciTech Connect

    Tilikin, I. N. Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-15

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  17. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    NASA Astrophysics Data System (ADS)

    Tilikin, I. N.; Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-01

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  18. Accurate Fourier transform infrared (FT-IR) spectroscopy measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) calibrated with synthetic spectra.

    PubMed

    Flores, Edgar; Viallon, Joële; Moussay, Philippe; Wielgosz, Robert Ian

    2013-10-01

    A novel method for determining the accuracy of laboratory-based measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) mole fractions using Fourier transform infrared (FT-IR) spectroscopy 1 cm(-1) resolution instruments calibrated with synthetic spectra has been developed. The traceability of these measurement results is to the reference line strength data contained within the high-resolution transmission molecular absorption (HITRAN) database. Incorporating a proper estimate of the uncertainty of this data into the measurement results will ensure that the SI traceable values are encompassed within the uncertainty of the measurement results. The major contributors to the uncertainties of the results are, in descending order of importance, the uncertainty in the line strength values (HITRAN 2004), the uncertainty attributed to the generation of reference spectra (including knowledge of the optical path length of the FT-IR gas cell), and temperature measurements of the gas. The stability of the FT-IR instrument itself is only a minor contributor to the overall uncertainty of the measurements. FT-IR measurements of NO2 mole fractions at nominal values of 10 μmol mol(-1) calibrated with synthetic spectra lead to standard uncertainties of 0.34 μmol mol(-1) (3.4% relative). In contrast, calibration of the FT-IR instrument with SI traceable gas standards generated by a dynamic weighing system resulted in measurements results with standard uncertainties of 0.04 μmol mol(-1) (0.4% relative). When comparing the consistency of measurement results based on the synthetic calibration method against those obtained by calibrations with SI traceable gas standards, the existence of a potential bias of ~5% was observed, although this was within the stated uncertainties of the results. The FT-IR measurements of HNO3 mole fractions at nominal values of 200 nmol mol(-1) calibrated with synthetic spectra resulted in values with standard uncertainties of 23 nmol mol(-1) (11

  19. Time-Resolved O3 Chemical Chain Reaction Kinetics Via High-Resolution IR Laser Absorption Methods

    NASA Technical Reports Server (NTRS)

    Kulcke, Axel; Blackmon, Brad; Chapman, William B.; Kim, In Koo; Nesbitt, David J.

    1998-01-01

    Excimer laser photolysis in combination with time-resolved IR laser absorption detection of OH radicals has been used to study O3/OH(v = 0)/HO2 chain reaction kinetics at 298 K, (i.e.,(k(sub 1) is OH + 03 yields H02 + 02 and (k(sub 2) is H02 + 03 yields OH + 202). From time-resolved detection of OH radicals with high-resolution near IR laser absorption methods, the chain induction kinetics have been measured at up to an order of magnitude higher ozone concentrations ([03] less than or equal to 10(exp 17) molecules/cu cm) than accessible in previous studies. This greater dynamic range permits the full evolution of the chain induction, propagation, and termination process to be temporally isolated and measured in real time. An exact solution for time-dependent OH evolution under pseudo- first-order chain reaction conditions is presented, which correctly predicts new kinetic signatures not included in previous OH + 03 kinetic analyses. Specifically, the solutions predict an initial exponential loss (chain "induction") of the OH radical to a steady-state level ([OH](sub ss)), with this fast initial decay determined by the sum of both chain rate constants, k(sub ind) = k(sub 1) + k(sub 2). By monitoring the chain induction feature, this sum of the rate constants is determined to be k(sub ind) = 8.4(8) x 10(exp -14) cu cm/molecule/s for room temperature reagents. This is significantly higher than the values currently recommended for use in atmospheric models, but in excellent agreement with previous results from Ravishankara et al.

  20. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A. ); Mitchell, G.E.; Dekoven, B.M. ); Yeh, A.T.; Gland, J.L. ); Moodenbaugh, A.R. )

    1993-01-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  1. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A.; Mitchell, G.E.; Dekoven, B.M.; Yeh, A.T.; Gland, J.L.; Moodenbaugh, A.R.

    1993-06-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  2. [The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

    PubMed

    Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

    2016-03-01

    Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results

  3. [Influence of silver/silicon dioxide on infrared absorption spectroscopy of sodium nitrate].

    PubMed

    Yang, Shi-Ling; Yue, Li; Jia, Zhi-Jun

    2014-09-01

    Quickly detecting of ocean nutrient was one important task in marine pollution monitoring. We discovered the application of surface-enhanced infrared absorption spectroscopy in the detection of ocean nutrient through researching the evaporation of sodium nitrate solution. The silicon dioxide (SiO2) with highly dispersion was prepared by Stober method, The silver/silica (Ag/SiO2) composite materials were prepared by mixing ammonia solution and silicon dioxide aqueous solution. Three kinds of composite materials with different surface morphology were fabricated through optimizing the experimental parameter and changing the experimental process. The surface morphology, crystal orientation and surface plasmon resonance were investigated by means of the scanning electronic microscope (SEM), X-ray diffraction (XRD), UV-Visible absorption spectrum and infrared ab- sorption spectroscopy. The SEM images showed that the sample A was purified SiO2, sample B and sample C were mixture of silver nanoparticle and silicon dioxide, while sample D was completed nanoshell structure. The absorption spectroscopy showed that there was surface plasmon resonance in the UV-visible region, while there was possibility of surface plasmon resonance in the Infrared absorption region. The effect of Ag/SiO2 composite material on the infrared absorption spectra of sodium nitrite solution was investigated through systematically analyzing the infrared absorption spectroscopy of sodium nitrate solution during its evaporation, i. e. the peak integration area of nitrate and the peak integration area of water molecule. The experimental results show that the integration area of nitrate was enhanced greatly during the evaporation process while the integration area of water molecule decreased continuously. The integration area of nitrate comes from the anti-symmetric stretch vibration and the enhancement of the vibration is attributed to the interface effect of Ag/SiO2 which is consistent with Jensen T

  4. Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

    ERIC Educational Resources Information Center

    Bazzi, Ali; Kreuz, Bette; Fischer, Jeffrey

    2004-01-01

    An experiment for determination of calcium in cereal using two-increment standard addition method in conjunction with flame atomic absorption spectroscopy (FAAS) is demonstrated. The experiment is intended to introduce students to the principles of atomic absorption spectroscopy giving them hands on experience using quantitative methods of…

  5. The temperature measurement research for high-speed flow based on tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Di, Yue; Jin, Yi; Jiang, Hong-liang; Zhai, Chao

    2013-09-01

    Due to the particularity of the high-speed flow, in order to accurately obtain its' temperature, the measurement system should has some characteristics of not interfereing with the flow, non-contact measurement and high time resolution. The traditional measurement method cannot meet the above requirements, however the measurement method based on tunable diode laser absorption spectroscopy (TDLAS) technology can meet the requirements for high-speed flow temperature measurement. When the near-infared light of a specific frequency is through the media to be measured, it will be absorbed by the water vapor molecules and then the transmission light intensity is detected by the detector. The temperature of the water vapor which is also the high-speed flow temperature, can be accurately obtained by the Beer-Lambert law. This paper focused on the research of absorption spectrum method for high speed flow temperature measurement with the scope of 250K-500K. Firstly, spectral line selection method for low temperature measurement of high-speed flow is discussed. Selected absorption lines should be isolated and have a high peak absorption within the range of 250-500K, at the same time the interference of the other lines should be avoided, so that a high measurement accuracy can be obtained. According to the near-infrared absorption spectra characteristics of water vapor, four absorption lines at the near 1395 nm and 1409 nm are selected. Secondly, a system for the temperature measurement of the water vapor in the high-speed flow is established. Room temperature are measured through two methods, direct absorption spectroscopy (DAS) and wavelength modulation spectroscopy (WMS) ,the results show that this system can realize on-line measurement of the temperature and the measurement error is about 3%. Finally, the system will be used for temperature measurement of the high-speed flow in the shock tunnel, its feasibility of measurement is analyzed.

  6. Strong-field induced dissociation dynamics in 1,2-dibromoethane traced by femtosecond XUV transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Chatterley, A. S.; Lackner, F.; Neumark, D. M.; Leone, S. R.; Gessner, O.

    2016-05-01

    Strong field induced dissociation dynamics of the small haloalkane 1,2-dibromoethane (DBE) have been explored using femtosecond XUV transient absorption spectroscopy. Dynamics are initiated by a near IR pump pulse with intensities between 75 and 220 TW cm-2, and are probed by the atomic site specific XUV absorption of the Br 3d levels. Immediately upon ionization, the spectral signatures of molecular ions appear. These molecular peaks decay in tandem with the appearance of atomic Br peaks in charge states of 0, + 1 and + 2, which are all monitored simultaneously. Neutral Br atoms are eliminated in 300 fs, presumably from statistical dissociation of vibrationally hot DBE+ ions, Br+ ions are eliminated in 70 fs from a more energetic dissociative ionization pathway, and Br++ ions are eliminated within the duration of the 35 fs pump pulse. The simultaneous recording of multiple parent molecule and fragment ion traces enables new insight into predominant dissociation pathways induced by strong field ionization of organic molecules.

  7. Background-free, highly sensitive surface-enhanced IR absorption of rhodamine 6G molecules deposited onto an array of microholes in thin silver film

    NASA Astrophysics Data System (ADS)

    Danilov, Pavel N.; Gonchukov, Sergey A.; Ionin, Andrey A.; Khmelnitskii, Roman A.; Kudryashov, Sergey I.; Nguyen, Trang T. H.; Rudenko, Andrey A.; Saraeva, Irina N.; Zayarny, Dmitry A.

    2016-05-01

    Selective IR absorption at 1261 cm-1 enhanced by 455 times, was demonstrated for rhodamine 6G molecules, covering a 2D-photonic crystal, represented by a regular array of 4-micron wide holes in a 30 nm thick silver film on a CaF2 substrate. The reference absorption lines were taken near 2900 cm-1, where the IR radiation is freely channeling through the microholes, indicating the reference substrate coverage by the dye molecules for its relative internal calibration. The limit of background-free detection for the analyte was determined at the level ~10-2 monolayer.

  8. Photocarrier dynamics in anatase TiO{sub 2} investigated by pump-probe absorption spectroscopy

    SciTech Connect

    Matsuzaki, H. E-mail: okamotoh@k.u-tokyo.ac.jp; Matsui, Y.; Uchida, R.; Yada, H.; Terashige, T.; Li, B.-S.; Sawa, A.; Kawasaki, M.; Tokura, Y.; Okamoto, H. E-mail: okamotoh@k.u-tokyo.ac.jp

    2014-02-07

    The dynamics of photogenerated electrons and holes in undoped anatase TiO{sub 2} were studied by femtosecond absorption spectroscopy from the visible to mid-infrared region (0.1–2.0 eV). The transient absorption spectra exhibited clear metallic responses, which were well reproduced by a simple Drude model. No mid-gap absorptions originating from photocarrier localization were observed. The reduced optical mass of the photocarriers obtained from the Drude-model analysis is comparable to theoretically expected one. These results demonstrate that both photogenerated holes and electrons act as mobile carriers in anatase TiO{sub 2}. We also discuss scattering and recombination dynamics of photogenerated electrons and holes on the basis of the time dependence of absorption changes.

  9. Configurational and conformational analysis of chiral molecules using IR and VCD spectroscopies: spiropentylcarboxylic acid methyl ester and spiropentyl acetate.

    PubMed

    Devlin, F J; Stephens, P J; Osterle, C; Wiberg, K B; Cheeseman, J R; Frisch, M J

    2002-11-15

    The chiral monosubstituted derivatives of spiropentane, spiropentylcarboxylic acid methyl ester, 1, and spiropentyl acetate, 2, have been synthesized in optically active form. Configurational and conformational analysis of 1 and 2 has been carried out using infrared (IR) and vibrational circular dichroism (VCD) spectroscopies. Analysis of the experimental IR and VCD spectra has been carried out using ab initio density functional theory (DFT). For both 1 and 2, DFT predicts two populated conformations. Comparison to experiment of the conformationally averaged IR and VCD spectra of 1 and 2, predicted using DFT, provides unequivocal evidence of the predicted conformations and yields the absolute configurations R(-)/S(+) for 1 and R(+)/S(-) for 2. These absolute configurations are consistent with the R(-)/S(+) absolute configuration of spiropentylcarboxylic acid, assigned previously via X-ray crystallography of its alpha-phenylethylammonium salt. PMID:12423137

  10. Rapid evaluation and quantitative analysis of thyme, origano and chamomile essential oils by ATR-IR and NIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Schulz, Hartwig; Quilitzsch, Rolf; Krüger, Hans

    2003-12-01

    The essential oils obtained from various chemotypes of thyme, origano and chamomile species were studied by ATR/FT-IR as well as NIR spectroscopy. Application of multivariate statistics (PCA, PLS) in conjunction with analytical reference data leads to very good IR and NIR calibration results. For the main essential oil components (e.g. carvacrol, thymol, γ-terpinene, α-bisabolol and β-farnesene) standard errors are in the range of the applied GC reference method. In most cases the multiple coefficients of determination ( R2) are >0.97. Using the IR fingerprint region (900-1400 cm -1) a qualitative discrimination of the individual chemotypes is possible already by visual judgement without to apply any chemometric algorithms.The described rapid and non-destructive methods can be applied in industry to control very easily purifying, blending and redistillation processes of the mentioned essential oils.

  11. Differentiation of Body Fluid Stains on Fabrics Using External Reflection Fourier Transform Infrared Spectroscopy (FT-IR) and Chemometrics.

    PubMed

    Zapata, Félix; de la Ossa, Ma Ángeles Fernández; García-Ruiz, Carmen

    2016-04-01

    Body fluids are evidence of great forensic interest due to the DNA extracted from them, which allows genetic identification of people. This study focuses on the discrimination among semen, vaginal fluid, and urine stains (main fluids in sexual crimes) placed on different colored cotton fabrics by external reflection Fourier transform infrared spectroscopy (FT-IR) combined with chemometrics. Semen-vaginal fluid mixtures and potential false positive substances commonly found in daily life such as soaps, milk, juices, and lotions were also studied. Results demonstrated that the IR spectral signature obtained for each body fluid allowed its identification and the correct classification of unknown stains by means of principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA). Interestingly, results proved that these IR spectra did not show any bands due to the color of the fabric and no substance of those present in daily life which were analyzed, provided a false positive. PMID:26896150

  12. Sensing properties of multiwalled carbon nanotubes grown in MW plasma torch: electronic and electrochemical behavior, gas sensing, field emission, IR absorption.

    PubMed

    Majzlíková, Petra; Sedláček, Jiří; Prášek, Jan; Pekárek, Jan; Svatoš, Vojtěch; Bannov, Alexander G; Jašek, Ondřej; Synek, Petr; Eliáš, Marek; Zajíčková, Lenka; Hubálek, Jaromír

    2015-01-01

    Vertically aligned multi-walled carbon nanotubes (VA-MWCNTs) with an average diameter below 80 nm and a thickness of the uniform VA-MWCNT layer of about 16 µm were grown in microwave plasma torch and tested for selected functional properties. IR absorption important for a construction of bolometers was studied by Fourier transform infrared spectroscopy. Basic electrochemical characterization was performed by cyclic voltammetry. Comparing the obtained results with the standard or MWCNT‑modified screen-printed electrodes, the prepared VA-MWCNT electrodes indicated their high potential for the construction of electrochemical sensors. Resistive CNT gas sensor revealed a good sensitivity to ammonia taking into account room temperature operation. Field emission detected from CNTs was suitable for the pressure sensing application based on the measurement of emission current in the diode structure with bending diaphragm. The advantages of microwave plasma torch growth of CNTs, i.e., fast processing and versatility of the process, can be therefore fully exploited for the integration of surface-bound grown CNTs into various sensing structures. PMID:25629702

  13. Sensing Properties of Multiwalled Carbon Nanotubes Grown in MW Plasma Torch: Electronic and Electrochemical Behavior, Gas Sensing, Field Emission, IR Absorption

    PubMed Central

    Majzlíková, Petra; Sedláček, Jiří; Prášek, Jan; Pekárek, Jan; Svatoš, Vojtěch; Bannov, Alexander G.; Jašek, Ondřej; Synek, Petr; Eliáš, Marek; Zajíčková, Lenka; Hubálek, Jaromír

    2015-01-01

    Vertically aligned multi-walled carbon nanotubes (VA-MWCNTs) with an average diameter below 80 nm and a thickness of the uniform VA-MWCNT layer of about 16 μm were grown in microwave plasma torch and tested for selected functional properties. IR absorption important for a construction of bolometers was studied by Fourier transform infrared spectroscopy. Basic electrochemical characterization was performed by cyclic voltammetry. Comparing the obtained results with the standard or MWCNT‐modified screen-printed electrodes, the prepared VA-MWCNT electrodes indicated their high potential for the construction of electrochemical sensors. Resistive CNT gas sensor revealed a good sensitivity to ammonia taking into account room temperature operation. Field emission detected from CNTs was suitable for the pressure sensing application based on the measurement of emission current in the diode structure with bending diaphragm. The advantages of microwave plasma torch growth of CNTs, i.e., fast processing and versatility of the process, can be therefore fully exploited for the integration of surface-bound grown CNTs into various sensing structures. PMID:25629702

  14. Proteolytically-induced changes of secondary structural protein conformation of bovine serum albumin monitored by Fourier transform infrared (FT-IR) and UV-circular dichroism spectroscopy

    NASA Astrophysics Data System (ADS)

    Güler, Günnur; Vorob'ev, Mikhail M.; Vogel, Vitali; Mäntele, Werner

    2016-05-01

    Enzymatically-induced degradation of bovine serum albumin (BSA) by serine proteases (trypsin and α-chymotrypsin) in various concentrations was monitored by means of Fourier transform infrared (FT-IR) and ultraviolet circular dichroism (UV-CD) spectroscopy. In this study, the applicability of both spectroscopies to monitor the proteolysis process in real time has been proven, by tracking the spectral changes together with secondary structure analysis of BSA as proteolysis proceeds. On the basis of the FTIR spectra and the changes in the amide I band region, we suggest the progression of proteolysis process via conversion of α-helices (1654 cm- 1) into unordered structures and an increase in the concentration of free carboxylates (absorption of 1593 and 1402 cm- 1). For the first time, the correlation between the degree of hydrolysis and the concentration of carboxylic groups measured by FTIR spectroscopy was revealed as well. The far UV-CD spectra together with their secondary structure analysis suggest that the α-helical content decreases concomitant with an increase in the unordered structure. Both spectroscopic techniques also demonstrate that there are similar but less spectral changes of BSA for the trypsin attack than for α-chymotrypsin although the substrate/enzyme ratio is taken the same.

  15. [The effect of Tween-80 on the differentiation of Trichophyton mentagrophytes and Trichophyton rubrum strains with FT-IR spectroscopy].

    PubMed

    Ergın, Çagri; İlkit, Macit; Gök, Yaşar; Çon, Ahmet Hilmi; Özel, Mustafa Zafer; Kabay, Nilgün; Döğen, Aylin; Baygu, Yasemin

    2014-07-01

    Trichophyton mentagrophytes and Trichophyton rubrum, are two of the frequently identified dermatophyte species in routine microbiology laboratories. Although newer technologies may assist in species-level identification, direct application of these methods usually require improvement in order to obtain reliable identification of these species. Earlier data have shown that dermatophytes may be identified with FT-IR spectroscopy although there are some limitations. In particular, the organic bond ranges in FT-IR spectra showed more irregularity because of the eucaryotic complexity of the molds. In this study, Tween-80 which is an inorganic molecule, was added to the dermatophyte growth medium in order to investigate its effect on FT-IR spectroscopy analysis of dermatophytes. Nine reference dermatophyte strains [5 T.mentagrophytes complex (T.asteroides CBS 424.63, T.erinacei CBS 344.79, CBS 511.73, CBS 677.86, T.mentagrophytes CBS 110.65) and 4 T.rubrum complex strains with different morphotypes (T.fluviomuniense CBS 592.68, T.kuryangei CBS 422.67, T.raubitschekii CBS 102856, T.rubrum CBS 392.58)] were included in the study. All strains were cultured on Sabouraud glucose agar either with or without 1% Tween-80 for three weeks. After the incubation period, superficial scrapings from each dermatophyte colony were analyzed using FT-IR spectroscopy. All measurements were performed in transmission mode between 4400 and 400 cm-1. Numerous spectral window data were analyzed by principal component analysis and hierarchical clustering was performed. The second derivations of spectral ranges revealed clear grouping of T.mentagrophytes complex and T.rubrum complex in association over five separate spectral ranges. The findings also showed that while all of the T.mentagrophytes strains contained lipid compounds in their mold structure after Tween-80 incubation (p< 0.025), T.rubrum strains did not. Based on these results, it was concluded that culture medium containing Tween-80

  16. Minute Concentration Measurements of Simple Hydrocarbon Species Using Supercontinuum Laser Absorption Spectroscopy.

    PubMed

    Yoo, Jihyung; Traina, Nicholas; Halloran, Michael; Lee, Tonghun

    2016-06-01

    Minute concentration measurements of simple hydrocarbon gases are demonstrated using near-infrared supercontinuum laser absorption spectroscopy. Absorption-based gas sensors, particularly when combined with optical fiber components, can significantly enhance diagnostic capabilities to unprecedented levels. However, these diagnostic techniques are subject to limitations under certain gas sensing applications where interference and harsh conditions dominate. Supercontinuum laser absorption spectroscopy is a novel laser-based diagnostic technique that can exceed the above-mentioned limitations and provide accurate and quantitative concentration measurement of simple hydrocarbon species while maintaining compatibility with telecommunications-grade optical fiber components. Supercontinuum radiation generated using a highly nonlinear photonic crystal fiber is used to probe rovibrational absorption bands of four hydrocarbon species using full-spectral absorption diagnostics. Absorption spectra of methane (CH4), acetylene (C2H2), and ethylene (C2H4) were measured in the near-infrared spectrum at various pressures and concentrations to determine the accuracy and feasibility of the diagnostic strategy. Absorption spectra of propane (C3H8) were subsequently probed between 1650 nm and 1700 nm, to demonstrate the applicability of the strategy. Measurements agreed very well with simulated spectra generated using the HITRAN database as well as with previous experimental results. Absorption spectra of CH4, C2H2, and C2H4 were then analyzed to determine their respective measurement accuracy and detection limit. Concentration measurements integrated from experimental results were in very good agreement with independent concentration measurements. Calculated detection limits of CH4, C2H2, and C2H4 at room temperature and atmospheric pressure are 0.1%, 0.09%, and 0.17%, respectively. PMID:27091905

  17. Aminophenol isomers unraveled by conformer-specific far-IR action spectroscopy.

    PubMed

    Yatsyna, Vasyl; Bakker, Daniël J; Feifel, Raimund; Rijs, Anouk M; Zhaunerchyk, Vitali

    2016-02-17

    Spectroscopic studies of molecular structure can strongly benefit from extending the conventional mid-IR range to the far-IR and THz regions, as low-frequency molecular vibrations provide unique fingerprints and high sensitivity to intra- and intermolecular interactions. In this work, the gas-phase conformer specific far-IR spectra of aminophenol isomers, recorded in the spectral range of 220-800 cm(-1) at the free-electron laser laboratory FELIX in Nijmegen (the Netherlands), are reported. Many distinct far-IR vibrational signatures which are specific for the molecular structure of the different aminophenol isomers are revealed and assigned. The observed far-IR transitions of the NH2 wagging (inversion) motion have been treated with a double-minimum harmonic well potential model that has enabled us to obtain the inversion barrier values. Moreover, we discuss the limitations and capability of conventional DFT frequency calculations to describe the far-IR vibrational modes. PMID:26854118

  18. FT-IR spectroscopy of microorganisms at the Robert Koch Institute: experiences gained during a successful project

    NASA Astrophysics Data System (ADS)

    Naumann, Dieter

    2008-02-01

    The characterization and identification of microorganisms by infrared or Raman spectroscopy is probably one of the best developed and most frequent applications of biomedical vibrational spectroscopy. The serial types of dedicated instruments for routine FT-IR characterizations of microorganisms are now available on the market and already used in routine microbiological laboratories. The experiences gained to date, especially the necessity to define standards for sampling and measurement procedures and the details of how data compatibility between different laboratories is achieve will be discussed as well as the problem to establish validated reference data bases for objective species or strain identifications.

  19. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy

    SciTech Connect

    Grunwaldt, Jan-Dierk; Kimmerle, Bertram; Baiker, Alfons; Boye, Pit; Schroer, Christian G.; Glatzel, Pieter; Borca, Camelia N.; Beckmann, Felix

    2009-09-25

    Spectroscopic studies on heterogeneous catalysts have mostly been done in an integral mode. However, in many cases spatial variations in catalyst structure can occur, e.g. during impregnation of pre-shaped particles, during reaction in a catalytic reactor, or in microstructured reactors as the present overview shows. Therefore, spatially resolved molecular information on a microscale is required for a comprehensive understanding of theses systems, partly in ex situ studies, partly under stationary reaction conditions and in some cases even under dynamic reaction conditions. Among the different available techniques, X-ray absorption spectroscopy (XAS) is a well-suited tool for this purpose as the different selected examples highlight. Two different techniques, scanning and full-field X-ray microscopy/tomography, are described and compared. At first, the tomographic structure of impregnated alumina pellets is presented using full-field transmission microtomography and compared to the results obtained with a scanning X-ray microbeam technique to analyse the catalyst bed inside a catalytic quartz glass reactor. On the other hand, by using XAS in scanning microtomography, the structure and the distribution of Cu(0), Cu(I), Cu(II) species in a Cu/ZnO catalyst loaded in a quartz capillary microreactor could be reconstructed quantitatively on a virtual section through the reactor. An illustrating example for spatially resolved XAS under reaction conditions is the partial oxidation of methane over noble metal-based catalysts. In order to obtain spectroscopic information on the spatial variation of the oxidation state of the catalyst inside the reactor XAS spectra were recorded by scanning with a micro-focussed beam along the catalyst bed. Alternatively, full-field transmission imaging was used to efficiently determine the distribution of the oxidation state of a catalyst inside a reactor under reaction conditions. The new technical approaches together with quantitative data

  20. Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

    PubMed Central

    Klein, Alexander; Witzel, Oliver; Ebert, Volker

    2014-01-01

    We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS) with the enhanced noise rejection of wavelength modulation spectroscopy (WMS). In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS) spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS) and an additional 20 kHz sinusoidal modulation (WMS). The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 μm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K). A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer. PMID:25405508

  1. The application of the derivative IR-spectroscopy and HPLC-ESI-MS/MS in the analysis of archaeology resin

    NASA Astrophysics Data System (ADS)

    Zareva, S.; Kuleff, I.

    2010-07-01

    The applicability of the reducing-difference procedure for the interpretation of the conventional IR-spectroscopy as successful scientific technique for the analysis of ancient and modern resins has been demonstrated. The new temperature tool for modeling of the ancient resin samples has also been shown. The experimental infrared data are supported by the hydride approach of HPLC-MS-MS with ES-ionisation.

  2. Near-IR Spectroscopy and Visual Broadband Photometry of Unbound Asteroid Pairs

    NASA Astrophysics Data System (ADS)

    Wolters, Stephen D.; Weissman, P.; Duddy, S. R.; Christou, A.; Green, S. F.; Lowry, S. C.; Rozitis, B.

    2012-10-01

    Over 62 pairs of asteroids have been identified with extremely similar orbits (Rozek, Breiter, and Jopek 2011, MNRAS 412, 987). Backwards integration of their orbits show that each pair probably experienced a very low-velocity close encounter, in many cases less than 1 Myr ago (e.g. Vokrouhlický and Nesvorný 2008, AJ 136, 280). Pravec et al. (2010, Nature, 466, 1085) examined 35 pairs and found that the secondary/primary mass ratio is <0.2. Also, as this ratio approaches 0.2, the rotation period of the primary increases. This is consistent with formation of the pairs through rotational fission of a parent rubble-pile asteroid (Scheeres 2007, Icarus 189, 370). However, the pairs were linked through dynamical considerations alone, and mass ratios were determined using catalogued visual magnitudes and the assumption that the albedos and bulk densities of the components are identical. We are undertaking a campaign of characterising the asteroids in these pairs using visual and NIR spectroscopy as well as thermal IR photometry. We present 0.8-2.5 micron spectroscopic observations of using SpeX on NASA-IRTF, and BVRI photometry using the 0.6-m Table Mountain Observatory telescope. Our goals are to assess the similarity of the spectra of the components’ surfaces (e.g. Duddy et al. 2012, A&A, 539, A36) and also to look for evidence of color variation as a function of rotational phase. Since dynamical studies have placed constraints on the formation ages, if the asteroids are completely resurfaced during formation, we can start to explore the timescales involved in space weathering. We report recent progress in our investigations. This work was supported in part by the NASA Planetary Astronomy Program and done in part at the Jet Propulsion Laboratory under contract with NASA.

  3. Fatty Acid Chain Length Dependence of Phase Separation Kinetics in Stratum Corneum Models by IR Spectroscopy.

    PubMed

    Mendelsohn, Richard; Rabie, Emann; Walters, Russel M; Flach, Carol R

    2015-07-30

    The main barrier to permeability in human skin resides in the stratum corneum (SC), a layered structure consisting of anucleated, flattened cells (corneocytes) embedded in a heterogeneous lamellar lipid matrix. While lipid structures and packing propensities in the SC and in SC models have been extensively investigated, only limited data are available concerning the kinetics and mechanism of formation of lamellar phases and particular lipid packing motifs. In our prior investigation, kinetic IR spectroscopy measurements probed the temporal sequence of phase separation leading to ordered structures in a three component SC model of equimolar structurally heterogeneous ceramide[NS], chain perdeuterated stearic acid, and cholesterol. In the current work, the phase separation kinetic effects of specific fatty acid chain lengths with a synthetic structurally homogeneous ceramide[NS] in similar ternary mixtures are examined. These are compared with a mixture containing ceramide[NS] with an unsaturated acid chain. The kinetic events are sensitive to the difference in chain lengths between the ceramide acid chain and the fatty acid as well as to the presence of unsaturation in the former. The observed kinetic behaviors span a wide range of phase separation times, ranging from the formation of a solid solution stable for at least 200 h, to a system in which an orthorhombic fatty acid structure is essentially completely formed within the time resolution of the experiment (15 min). The data seem to offer some features of a spinodal phase separation at relatively short times. Overall the approach offers a possible means for addressing several unanswered questions pertinent to skin pharmacology, such as the roles of a wide variety of ceramide and fatty acid species and the design of therapeutic interventions for repair of pathological conditions of the SC. PMID:26131756

  4. IGRINS Near-IR High-resolution Spectroscopy of Multiple Jets around LkHα 234

    NASA Astrophysics Data System (ADS)

    Oh, Heeyoung; Pyo, Tae-Soo; Yuk, In-Soo; Park, Byeong-Gon; Park, Chan; Chun, Moo-Young; Pak, Soojong; Kim, Kang-Min; Sok Oh, Jae; Jeong, Ueejeong; Yu, Young Sam; Lee, Jae-Joon; Kim, Hwihyun; Hwang, Narae; Kaplan, Kyle; Pavel, Michael; Mace, Gregory; Lee, Hye-In; Nguyen Le, Huynh Anh; Lee, Sungho; Jaffe, Daniel T.

    2016-02-01

    We present the results of high-resolution near-IR spectroscopy toward the multiple outflows around the Herbig Be star LkHα 234 using the Immersion Grating Infrared Spectrograph. Previous studies indicate that the region around LkHα 234 is complex, with several embedded young stellar objects and the outflows associated with them. In simultaneous H- and K-band spectra from HH 167, we detected 5 [Fe ii] and 14 H2 emission lines. We revealed a new [Fe ii] jet driven by radio continuum source VLA 3B. Position-velocity diagrams of the H2 1-0 S(1) λ2.122 μm line show multiple velocity peaks. The kinematics may be explained by a geometrical bow shock model. We detected a component of H2 emission at the systemic velocity (VLSR = -10.2 km s-1) along the whole slit in all slit positions, which may arise from the ambient photodissociation region. Low-velocity gas dominates the molecular hydrogen emission from knots A and B in HH 167, which is close to the systemic velocity; [Fe ii] emission lines are detected farther from the systemic velocity, at VLSR = -100--130 km s-1. We infer that the H2 emission arises from shocked gas entrained by a high-velocity outflow. Population diagrams of H2 lines imply that the gas is thermalized at a temperature of 2500-3000 K and the emission results from shock excitation. This paper includes data taken at The McDonald Observatory of The University of Texas at Austin.

  5. Watching a protein as it functions with picosecond X-ray crystallography and femtosecond IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Anfinrud, Philip

    2003-03-01

    Proteins are engaged in a myriad of tasks that are essential to life. To understand in mechanistic detail how proteins function, it is crucial to know the time ordering of events that give rise to their designed (or modified) function. Myoglobin (Mb), a ligand-binding heme protein, has long served as a model system for investigating ligand transport and binding in proteins. Using femtosecond time-resolved polarized IR spectroscopy, the dynamics of ligand motion after photodetachment of CO from MbCO have been probed. These studies reveal the time-dependent orientation of CO, the existence of a docking site that mediates the transport of ligands to and from the active binding site, as well as the dynamics of ligand binding and escape. To probe the structural evolution of a protein as it executes its function, a multinational collaboration has been established to acquire time-resolved X-ray crystal structures on the ID09B beam line at the European Synchrotron and Radiation Facility. Recent improvements in the experimental methodology have extended the time resolution down to 150 picoseconds and improved the spatial resolution of the electron density maps to below 2 Å. Using this technique, we have acquired time-resolved high resolution structures of L29F-MbCO, a mutant of myoglobin that exhibits unusually rapid ligand migration dynamics. The frame-by-frame structural evolution allows us to literally "watch" this protein as it functions. Conformational changes far more dramatic than the structural differences between the carboxy and deoxy states are observed. The correlated motion of CO and several side chains provides a structural explanation for the rapid expulsion of toxic CO from the nearby ligand docking site.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  7. Studies of the residual absorption of HTSC at submillimeter wavelengths by means of photothermal interference spectroscopy

    SciTech Connect

    Barowski, H.S.; Arnold, A.; Eder, R.

    1996-12-31

    The determination of the residual, low temperature absorption of high temperature superconductors is of interest for applications of this new materials at submillimeter wavelengths and of basic interest. The photothermal interference spectroscopy allows to measure the residual, low temperature absorption of a HTSC. For the determination of the residual absorption of a superconductor a far-infrared beam is periodically modulated and focused on the sample. Absorption leads to a periodic change of the temperature of the sample surface and, due to heat diffusion, also in the gas volume adjacent to the sample. This temperature change in the gas is detected via the refractive index change using a two beam interferometer. The authors studied the residual losses of YBaCuO thin films on various substrates and of BiSrCaCuO (2212) single crystals at submillimeter wavelengths. They find that the frequency dependence of the absorptivity, which shows a frequency squared behavior at microwave frequencies, is less than quadratic at THz-frequencies. The YBaCuO thin films show a plateau between 0.6 THz and 4 THz with an absolute value of the absorptivity of about 10{sup {minus}2}. A BiSrCaCuO single crystal shows a plateau between 1 THz and 4 THz with an absorptivity in the order of 10{sup {minus}3}.

  8. Infrared-laser spectroscopy using a long-pathlength absorption cell

    SciTech Connect

    Kim, K.C.; Briesmeister, R.A.

    1983-01-01

    The absorption measurements in an ordinary cell may require typically a few torr pressure of sample gas. At these pressures the absorption lines are usually pressure-broadened and, therefore, closely spaced transitions are poorly resolved even at diode-laser resolution. This situation is greatly improved in Doppler-limited spectroscopy at extremely low sample pressures. Two very long-pathlength absorption cells were developed to be used in conjunction with diode lasers. They were designed to operate at controlled temperatures with the optical pathlength variable up to approx. 1.5 km. Not only very low sample pressures are used for studies with such cells but also the spectroscopic sensitivity is enhanced over conventional methods by a factor of 10/sup 3/ to 10/sup 4/, improving the analytical capability of measuring particle densities to the order of 1 x 10'' molecules/cm/sup 3/. This paper presents some analytical aspects of the diode laser spectroscopy using the long-pathlength absorption cells in the areas of absorption line widths, pressure broadening coefficients, isotope composition measurements and trace impurity analysis.

  9. Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopy

    SciTech Connect

    Attar, Andrew R.; Blumling, Daniel E.; Knappenberger, Kenneth L. Jr.

    2011-01-14

    Steady-state and time-resolved spectroscopies were employed to study the photodissociation of both the neutral (HS-CH{sub 2}-COOH) and doubly deprotonated ({sup -}S-CH{sub 2}-COO{sup -}) forms of thioglycolic acid (TGA), a common surface-passivating ligand used in the aqueous synthesis and organization of semiconducting nanostructures. Room temperature UV-Vis absorption spectroscopy indicated strong absorption by the S{sub 1} and S{sub 2} excited states at 250 nm and 185 nm, respectively. The spectrum also contained a weaker absorption band that extended to approximately 550 nm, which was assigned to the {pi}{sub CO}{sup *}(leftarrow)n{sub O} transition. Femtosecond time-resolved transient absorption spectroscopy was performed on TGA using 400 nm excitation and a white-light continuum probe to provide the temporally and spectrally resolved data. Both forms of TGA underwent a photoinduced dissociation from the excited state to form an {alpha}-thiol-substituted acyl radical ({alpha}-TAR, S-CH{sub 2}-CO). For the acidic form of TGA, radical formation occurred with an apparent time constant of 60 {+-} 5 fs; subsequent unimolecular decay took 400 {+-} 60 fs. Similar kinetics were observed for the deprotonated form of TGA (70 {+-} 10 fs radical formation; 420 {+-} 40 fs decay). The production of the {alpha}-TAR was corroborated by the observation of its characteristic optical absorption. Time-resolved data indicated that the photoinduced dissociation of TGA via cleavage of the C-OH bond occurred rapidly ({<=}100 fs). The prevalence of TGA in aqueous semiconducting nanoparticles makes its absorption in the visible spectral region and subsequent dissociation key to understanding the behavior of nanoscale systems.

  10. Hydrogenated graphene on Ir(111): A high-resolution electron energy loss spectroscopy study of the vibrational spectrum

    NASA Astrophysics Data System (ADS)

    Kyhl, Line; Balog, Richard; Angot, Thierry; Hornekær, Liv; Bisson, Régis

    2016-03-01

    Hydrogen atom adsorption on high-quality graphene on Ir(111) [gr/Ir(111)] is investigated using high-resolution electron energy loss spectroscopy. The evolution of the vibrational spectrum, up to 400 meV, of gr/Ir(111) upon increasing hydrogen atom exposures is measured. The two dominant binding configurations of atomic hydrogen are identified as (1) graphanelike hydrogen clusters on the parts of the graphene more strongly interacting with the Ir(111) surface and (2) dimers bound more weakly to the freestanding parts of the graphene. The graphanelike surface structures lead to increased corrugation of the graphene sheet, yielding graphane-related phonon components. Additionally, a recent theoretical prediction of the existence of a bending character for a LO/TO graphane chair phonon mode is experimentally verified. No clear evidence was found for hydrogen bound on both sides of a high-quality graphene sheet and phonon features strongly suggest interactions between graphanelike hydrogen clusters and Ir atoms in the substrate.

  11. Far-IR Absorption Features of Titan Aerosol Analogs Produced from Aromatic Precursors

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua; Trainer, M. G.; Anderson, C. M.; Loeffler, M. J.

    2012-10-01

    The arrival of the Cassini spacecraft in orbit around Saturn has led to the discovery of benzene (C6H6) at ppm levels, as well as large positive ions in Titan’s atmosphere, tentatively identified as polycyclic aromatic hydrocarbons (PAHs).[1] The presence of aromatic molecules, which are photolytically active in the ultraviolet, may be an important part of the formation of aerosol particles in Titan’s haze layers, even at these low concentrations. To date, there have been no laboratory experiments in the literature exploring this area of study. The analysis of data from the Composite Infrared Spectrometer (CIRS) on-board Cassini has recently uncovered a broad emission feature centered at 140 cm-1 in the far-IR that is unique to the aerosol layers of Titan’s atmosphere.[2] Current optical constants from laboratory-generated aerosol analogs have been unable to reproduce this feature.[3,4] From the broadness of this feature, we speculate that the emission is a blended composite of low-energy vibrations of large molecules such as PAHs and their nitrogen containing counterparts, polycyclic aromatic nitrogen heterocycles (PANHs). We hypothesize that the inclusion of trace amounts of aromatic precursors will aid in the production of these large structures in the laboratory-generated aerosols. In this study, we perform UV irradiation of several aromatic precursors, both with and without nitrogen heteroatoms, to understand their influence on the observable characteristics of the aerosol. Measured optical and chemical properties will be compared to those formed from CH4/N2 mixtures [5,6] as well as to those from Cassini observations. [1] Waite, J. H., et al. (2007) Science 316 870-875. [2] Anderson, C.M, et al. (2011) Icarus 212 762-778. [3] Khare, B.N., et al. (1984) Icarus 60 127-137. [4] Imanaka, H., et al. (2012) Icarus 218 247-261. [5] Trainer, M.G., et al. (2006) PNAS 103 18035-18042. [6] Trainer, M.G., et al. (2012) Astrobiology 12 315-326.

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

    NASA Astrophysics Data System (ADS)

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

    2002-04-01

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

  13. First calibration measurements of an FTIR absorption spectroscopy system for liquid hydrogen isotopologues for the isotope separation system of fusion power plants

    SciTech Connect

    Groessle, R.; Beck, A.; Bornschein, B.; Fischer, S.; Kraus, A.; Mirz, S.; Rupp, S.

    2015-03-15

    Fusion facilities like ITER and DEMO will circulate huge amounts of deuterium and tritium in their fuel cycle with an estimated throughput of kg per hour. One important capability of these fuel cycles is to separate the hydrogen isotopologues (H{sub 2}, D{sub 2}, T{sub 2}, HD, HT, DT). For this purpose the Isotope Separation System (ISS), using cryogenic distillation, as part of the Tritium Enrichment Test Assembly (TRENTA) is under development at Tritium Laboratory Karlsruhe. Fourier transform infrared absorption spectroscopy (FTIR) has been selected to prove its capability for online monitoring of the tritium concentration in the liquid phase at the bottom of the distillation column of the ISS. The actual research-development work is focusing on the calibration of such a system. Two major issues are the identification of appropriate absorption lines and their dependence on the isotopic concentrations and composition. For this purpose the Tritium Absorption IR spectroscopy experiment has been set up as an extension of TRENTA. For calibration a Raman spectroscopy system is used. First measurements, with equilibrated mixtures of H{sub 2}, D{sub 2} and HD demonstrate that FTIR can be used for quantitative analysis of liquid hydro-gen isotopologues and reveal a nonlinear dependence of the integrated absorbance from the D{sub 2} concentration in the second vibrational branch of D{sub 2} FTIR spectra. (authors)

  14. Measurement of the absorption line profiles of water vapour isotopomers at 1.39 {mu}m using the methods of diode laser spectroscopy

    SciTech Connect

    Kuz'michev, A S; Nadezhdinskii, Aleksandr I; Ponurovskii, Ya Ya

    2011-07-31

    The issues related to high-precision measurement of the absorption line profiles of water vapour and its isotopomers using the methods of diode laser spectroscopy in the near IR range aimed at the analysis and detection of greenhouse gases are considered. The absorption line shape of H{sub 2}{sup 16}O is investigated as a function of pressure of different buffer gases. The influence of the instrument function of the diode laser (DL) on the precision of measuring the line profile is studied. From fitting the profile of Doppler-broadened H{sub 2}{sup 16}O absorption line to a model profile the lasing line width of the DL with a fibre pigtail is determined. The frequencies and intensities of absorption lines of water isotopomers H{sub 2}{sup 16}O, H{sub 2}{sup 17}O, H{sub 2}{sup 18}O, and HDO are measured in the range of DL oscillation. Analytical spectral regions are chosen for distant probing of water vapour using an airborne lab. (laser spectroscopy)

  15. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

    NASA Technical Reports Server (NTRS)

    Ferguson, Frank T.; Johnson, Natasha M.; Nuth, Joseph A., III

    2015-01-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

  16. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System.

    PubMed

    Ferguson, Frank T; Johnson, Natasha M; Nuth, Joseph A

    2015-10-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the High-Resolution Transmission Molecular Absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments. PMID:26449809

  17. The Non-Linear Relationship between Silicate Absorption Depth and IR Extinction in Dense Clouds

    NASA Astrophysics Data System (ADS)

    Chiar, Jean E.; Pendleton, Y.; Ennico, K.; Boogert, A.; Greene, T.; Lada, C.; Roellig, T.; Tielens, A.; Werner, M.; Whittet, D.

    2006-12-01

    Interstellar silicates are likely to be a part of all grains responsible for extinction in the diffuse interstellar medium (ISM) and dense clouds. A correlation between visual extinction (Av) and the depth of the 9.7 mu silicate feature (measured as optical depth, tau(9.7)) is expected if the dust species are well mixed. In the diffuse ISM, such a correlation is observed for lines of sight in the solar neighborhood. A previous study of the silicate absorption feature in the Taurus dark cloud showed a tendency for the correlation to break down at high Av (Whittet et al. 1988, MNRAS, 233, 321), but the scatter was large. We have acquired Spitzer Infrared Spectrograph data of several lines of sight in the IC 5146, Barnard 68, Chameleon I and Serpens dense clouds. To eliminate any uncertainties associated with adopting a specific extinction law, we investigated the relationship between tau(9.7) and E(J-K). Our data set spans E(J-K) between 0.3 and 8 mag (Av=between 2-35 mag.). All lines of sight show the 9.7 mu silicate feature. For E(J-K) greater than about 2 mag, tau(9.7) levels off, much like the trend observed in the Taurus data. There are two exceptions: one line of sight in Serpens, with E(J-K) 4 mag lies on the diffuse ISM line. Another line of sight with E(J-K) 8 mag, also in Serpens, lies well below the diffuse ISM line, but well above the “flat” trend of the other dense cloud sources. This particular line of sight also has a high ice column relative to the amount of visual/infrared extinction. The cause of the “flat” trend exhibited by most of the dense cloud points is undetermined. However, in general, it is unlikely that ice mantles would have any effect on the measured silicate feature since ices are transparent in the 10 mu region.

  18. Reactions of Highly Uniform Zeolite H-Supported Rhodium Complexes: Transient Characterization by Infrared and X-ray Absorption Spectroscopies

    SciTech Connect

    Ogino, I.; Gates, B

    2010-01-01

    A zeolite H-{beta}-supported mononuclear rhodium diethene complex (Rh(C{sub 2}H{sub 4}){sub 2}{l_brace}O{sub 2}Al{r_brace}, where the braces indicate a part of the zeolite) was formed by the reaction of Rh(acac)({eta}{sub 2}-C{sub 2}H{sub 4}){sub 2} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sub 2}{sup -}) with the zeolite. Transient characterization of the sample by X-ray absorption near edge structure (XANES) and infrared (IR) spectroscopies (combined with mass spectrometry of the effluent gas) while the sample was in contact with flowing CO indicates a simple stoichiometric conversion of the supported metal complex into another species, identified by the spectra as the zeolite-supported rhodium gem-dicarbonyl (Rh(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}). The sharpness of the v{sub CO} bands in the IR spectrum indicates a high degree of uniformity of the supported rhodium gem-dicarbonyl, and isosbestic points in the XANES spectra as the transformation was occurring imply that the rhodium diethene complex was also highly uniform. Spectra similarly show that treatment of the supported rhodium gem-dicarbonyl with flowing C{sub 2}H{sub 4} resulted in another stoichiometrically simple transformation, giving a species suggested to be Rh(C{sub 2}H{sub 4})(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}. The intermediate was ultimately transformed when the sample was purged with helium into another highly uniform supported species, inferred on the basis of IR spectra to be Rh(C{sub 2}H{sub 4})(CO){l_brace}O{sub 2}Al{r_brace}. Extended X-ray absorption fine structure spectra characterizing the supported rhodium diethene complex and the species formed from it show how the Rh-O bond distance at the Rh-support interface varied in response to the changes in the ligands bonded to the rhodium.

  19. Structure Determination and Excited State Proton Transfer Reaction of 1-NAPHTHOL-AMMONIA Clusters in the S_{1} State Studied by Uv-Ir Mid-Ir Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Shunpei; Miyazaki, Mitsuhiko; Martin, Weiler; Ishikawa, Haruki; Fujii, Masaaki

    2013-06-01

    1-naphthol ammonia clusters have been studied long time as a benchmark system of the excited state proton transfer (ESPT) reactions. Understanding the ESPT reaction in this system has still not been fully established. To detect the cluster size dependence of the S_{1} state properties, many researcher extensively investigated such as emission spectra, lifetime, solvents (ammonia) evaporation pattern. Curiously, cluster structure that is fundamental to discuss the reaction has not been determined for the system. Thus we applied an IR spectroscopy to the S_{1} states of the system to determine the cluster structure and to discuss the minimum size inducing the ionic dissociation of the O-H bond in the S_{1} state. IR spectra were recorded not only the O-H and N-H stretching region (3 {μ}m) but also the skeletal vibrational region (5.5-10 {μ}m). Though O-H and N-H stretching vibrations do not provide useful structural information due to the broadness, the skeletal vibrations hold the sharpness even in the S_{1} states. Changes in the skeletal vibrations due to the ammonia solvation, e.g. C-O stretching and C-O-H bending, will be discussed based on a comparison with theoretical calculations. O. Cheshnovsky and S. Leutwylar, J. Chem. Phys. 1, 4127 (1988). S. K. Kim et al., Chem. Phys. lett. 228, 369 (1994). C. Dedonder-Lardeux et al., Phys. Chem, Chem, Phys. 3, 4316 (2001).

  20. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

  1. Undistorted X-ray Absorption Spectroscopy Using s-Core-Orbital Emissions.

    PubMed

    Golnak, Ronny; Xiao, Jie; Atak, Kaan; Unger, Isaak; Seidel, Robert; Winter, Bernd; Aziz, Emad F

    2016-05-12

    Detection of secondary emissions, fluorescence yield (FY), or electron yield (EY), originating from the relaxation processes upon X-ray resonant absorption has been widely adopted for X-ray absorption spectroscopy (XAS) measurements when the primary absorption process cannot be probed directly in transmission mode. Various spectral distortion effects inherent in the relaxation processes and in the subsequent transportation of emitted particles (electron or photon) through the sample, however, undermine the proportionality of the emission signals to the X-ray absorption coefficient. In the present study, multiple radiative (FY) and nonradiative (EY) decay channels have been experimentally investigated on a model system, FeCl3 aqueous solution, at the excitation energy of the Fe L-edge. The systematic comparisons between the experimental spectra taken from various decay channels, as well as the comparison with the theoretically simulated Fe L-edge XA spectrum that involves only the absorption process, indicate that the detection of the Fe 3s → 2p partial fluorescence yield (PFY) gives rise to the true Fe L-edge XA spectrum. The two key characteristics generalized from this particular decay channel-zero orbital angular momentum (i.e., s orbital) and core-level emission-set a guideline for obtaining undistorted X-ray absorption spectra in the future. PMID:27101344

  2. Near-infrared spectrum of ZrF by intracavity laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Harms, Jack C.; O'Brien, Leah C.; Ni, Ann; Mahkdoom, Bilal; O'Brien, James J.

    2015-04-01

    The (1, 1) band of the CΩ = 3/2 - X2Δ3/2 transition of ZrF has been recorded at high resolution using intracavity laser absorption spectroscopy. The ZrF molecules were produced using a Zr-lined copper hollow cathode sputter source with a trace amount of SF6 as a fluoride source. Molecular constants from the analysis are presented and compared with previous work.

  3. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

  4. Third order nonlinear optical susceptibility of fluorescein-containing polymers determined by electro-absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gomez-Sosa, Gustavo; Beristain, Miriam F.; Ortega, Alejandra; Martínez-Viramontes, Jaquelin; Ogawa, Takeshi; Fernández-Hernández, Roberto C.; Tamayo-Rivera, Lis; Reyes-Esqueda, Jorge-Alejandro; Isoshima, Takashi; Hara, Masahiko

    2012-03-01

    Novel polymers containing xanthene groups with high dye concentrations were prepared, and their third order nonlinear optical properties were studied by electroabsorption spectroscopy technique. The polymers were amorphous with refractive indices above 1.6 in the non-resonant region. The UV-Visible absorption spectra indicate the fluoresceins molecules in the polymers are H-aggregated. They showed third order nonlinear susceptibility, χ(3) (-ω:ω, 0, 0), of 2.5-3.5 × 10-12 esu.

  5. Narrow-band, tunable, semiconductor-laser-based source for deep-UV absorption spectroscopy.

    PubMed

    Kliner, D A; Koplow, J P; Goldberg, L

    1997-09-15

    Tunable, narrow-bandwidth (<200-MHz), ~215-nm radiation was produced by frequency quadrupling the ~860-nm output of a high-power, pulsed GaAlAs tapered amplifier seeded by an external-cavity diode laser. Pulsing the amplifier increased the 860 nm?215 nm conversion efficiency by 2 orders of magnitude with respect to cw operation. Detection of nitric oxide and sulfur dioxide by high-resolution absorption spectroscopy was demonstrated. PMID:18188256

  6. Quantitation of vitamin B 12 by first-derivative absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Karşilayan, Huriye

    1996-08-01

    Quantitation of vitamin B 12 by first-derivative absorption spectroscopy is described. Peak-to-peak (355 nm to 370 nm) amplitudes were measured from the first derivative spectra. The method permits rapid determination of vitamin B 12, and increases the detection limit while decreasing interference by impurities. The effects of the majority of other absorbing macromolecules which may also be present in biological samples are eliminated or very considerably minimized by this method.

  7. Capturing Transient Electronic and Molecular Structures in Liquids by Picosecond X-Ray Absorption Spectroscopy

    SciTech Connect

    Gawelda, W.; Pham, V. T.; El Nahhas, A.; Kaiser, M.; Zaushitsyn, Y.; Bressler, C.; Chergui, M.; Johnson, S. L.; Grolimund, D.; Abela, R.; Hauser, A.

    2007-02-02

    We describe an advanced setup for time-resolved x-ray absorption fine structure (XAFS) Spectroscopy with picosecond temporal resolution. It combines an intense femtosecond laser source synchronized to the x-ray pulses delivered into the microXAS beamline of the Swiss Light Source (SLS). The setup is applied to measure the short-lived high-spin geometric structure of photoexcited aqueous Fe(bpy)3 at room temperature.

  8. In situ x-ray-absorption spectroscopy study of hydrogen absorption by nickel-magnesium thin films

    NASA Astrophysics Data System (ADS)

    Farangis, B.; Nachimuthu, P.; Richardson, T. J.; Slack, J. L.; Perera, R. C.; Gullikson, E. M.; Lindle, D. W.; Rubin, M.

    2003-02-01

    Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Codeposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied with Ni to Mg atomic ratio. Pure Mg films with Pd overlayers were converted to MgH2: The H atoms occupy regular sites as in bulk MgH2. Although optical switching was slow in the absence of Ni, the amount of H2 absorption was large. Incorporation of Ni in Mg films led to an increase in the speed of optical switching but decreased maximum transparency. Significant shifts in the Ni L3 and L2 peaks are consistent with strong interaction with hydrogen in the mixed films.

  9. X-RAY ABSORPTION SPECTROSCOPY OF YB3+-DOPED OPTICAL FIBERS

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

    Optical fibers doped with Ytterbium-3+ have become increasingly common in fiber lasers and amplifiers. Yb-doped fibers provide the capability to produce high power and short pulses at specific wavelengths, resulting in highly effective gain media. However, little is known about the local structure, distribution, and chemical coordination of Yb3+ in the fibers. This information is necessary to improve the manufacturing process and optical qualities of the fibers. Five fibers doped with Yb3+ were studied using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES), in addition to Yb3+ mapping. The Yb3+ distribution in each fiber core was mapped with 2D and 1D intensity scans, which measured X-ray fluorescence over the scan areas. Two of the five fibers examined showed highly irregular Yb3+ distributions in the core center. In four of the five fibers Yb3+ was detected outside of the given fiber core dimensions, suggesting possible Yb3+ diffusion from the core, manufacturing error, or both. X-ray absorption spectroscopy (XAS) analysis has so far proven inconclusive, but did show that the fibers had differing EXAFS spectra. The Yb3+ distribution mapping proved highly useful, but additional modeling and examination of fiber preforms must be conducted to improve XAS analysis, which has been shown to have great potential for the study of similar optical fi bers.

  10. Near-IR spectroscopy of the eruptive variable source V2493 Cyg (HBC 722)

    NASA Astrophysics Data System (ADS)

    Lorenzetti, D.; Efimova, N.; Larionov, V.; Arkharov, A.; Gorshanov, D.; Giannini, T.; Antoniucci, S.; Di Paola, A.

    2012-05-01

    As part of our near-IR spectroscopic monitoring program of EXor pre-Main sequence variables (Lorenzetti et al. 2009 ApJ 693, 1056) on-going at the AZT24 1m IR telescope (Campo Imperatore, Italy), we have recently (2012 May 11) obtained a low resolution (R~250) near-IR spectrum (0.8 - 2.5 μm) of the outbursting source V2493 Cyg (otherwise called HBC 722). Since its outburst in August 2009 (Miller et al.

  11. Long-path supercontinuum absorption spectroscopy for measurement of atmospheric constituents.

    PubMed

    Brown, David M; Shi, Kebin; Liu, Zhiwen; Philbrick, C R

    2008-06-01

    A supercontinuum source has been proposed as a new tool for measurement of minor species concentrations on long paths through the atmosphere. The present work describes results from recent experiments that demonstrate the potential for Differential Absorption Spectroscopy (DAS) and Spectral Pattern Recognition Differential Absorption Lidar (SPR-DIAL) measurements utilizing a supercontinuum source. As an initial example of this measurement approach, the results include the quantification of water vapor concentration through indoor and outdoor path absorption measurements using a collimated supercontinuum source. Experimental spectra are compared with equivalent simulations from MODTRAN??? versions 4 and 5 to examine the water vapor band between 1300 and 1500 nm to demonstrate the feasibility of the approach. PMID:18545560

  12. 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.

  13. Deep ultraviolet Raman spectroscopy: A resonance-absorption trade-off illustrated by diluted liquid benzene

    NASA Astrophysics Data System (ADS)

    Chadwick, C. T.; Willitsford, A. H.; Philbrick, C. R.; Hallen, H. D.

    2015-12-01

    The magnitude of resonance Raman intensity, in terms of the real signal level measured on-resonance compared to the signal level measured off-resonance for the same sample, is investigated using a tunable laser source. Resonance Raman enhancements, occurring as the excitation energy is tuned through ultraviolet absorption lines, are used to examine the 1332 cm-1 vibrational mode of diamond and the 992 cm-1 ring-breathing mode of benzene. Competition between the wavelength dependent optical absorption and the magnitude of the resonance enhancement is studied using measured signal levels as a function of wavelength. Two system applications are identified where the resonance Raman significantly increases the real signal levels despite the presence of strong absorption: characterization of trace species in laser remote sensing and spectroscopy of the few molecules in the tiny working volumes of near-field optical microscopy.

  14. UV and IR Spectroscopy of Cold H2O(+)-Benzo-Crown Ether Complexes.

    PubMed

    Inokuchi, Yoshiya; Ebata, Takayuki; Rizzo, Thomas R

    2015-11-12

    The H2O(+) radical ion, produced in an electrospray ion source via charge transfer from Eu(3+), is encapsulated in benzo-15-crown-5 (B15C5) or benzo-18-crown-6 (B18C6). We measure UV photodissociation (UVPD) spectra of the (H2O·B15C5)(+) and (H2O·B18C6)(+) complexes in a cold, 22-pole ion trap. These complexes show sharp vibronic bands in the 35 700-37 600 cm(-1) region, similar to the case of neutral B15C5 or B18C6. These results indicate that the positive charge in the complexes is localized on H2O, giving the forms H2O(+)·B15C5 and H2O(+)·B18C6, in spite of the fact that the ionization energy of B15C5 and B18C6 is lower than that of H2O. The formation of the H2O(+) complexes and the suppression of the H3O(+) production through the reaction of H2O(+) and H2O can be attributed to the encapsulation of hydrated Eu(3+) clusters by B15C5 and B18C6. On the contrary, the main fragment ions subsequent to the UV excitation of these complexes are B15C5(+) and B18C6(+) radical ions; the charge transfer occurs from H2O(+) to B15C5 and B18C6 after the UV excitation. The position of the band origin for the H2O(+)·B18C6 complex (36323 cm(-1)) is almost the same as that for Rb(+)·B18C6 (36315 cm(-1)); the strength of the intermolecular interaction of H2O(+) with B18C6 is similar to that of Rb(+). The spectral features of the H2O(+)·B15C5 complex also resemble those of the Rb(+)·B15C5 ion. We measure IR-UV spectra of these complexes in the CH and OH stretching region. Four conformers are found for the H2O(+)·B15C5 complex, but there is one dominant form for the H2O(+)·B18C6 ion. This study demonstrates the production of radical ions by charge transfer from multivalent metal ions, their encapsulation by host molecules, and separate detection of their conformers by cold UV spectroscopy in the gas phase. PMID:26491792

  15. Identification of different forms of cocaine and substances used in adulteration using near-infrared Raman spectroscopy and infrared absorption spectroscopy.

    PubMed

    Penido, Ciro A F O; Pacheco, Marcos Tadeu T; Zângaro, Renato A; Silveira, Landulfo

    2015-01-01

    Identification of cocaine and subsequent quantification immediately after seizure are problems for the police in developing countries such as Brazil. This work proposes a comparison between the Raman and FT-IR techniques as methods to identify cocaine, the adulterants used to increase volume, and possible degradation products in samples seized by the police. Near-infrared Raman spectra (785 nm excitation, 10 sec exposure time) and FT-IR-ATR spectra were obtained from different samples of street cocaine and some substances commonly used as adulterants. Freebase powder, hydrochloride powder, and crack rock can be distinguished by both Raman and FT-IR spectroscopies, revealing differences in their chemical structure. Most of the samples showed characteristic peaks of degradation products such as benzoylecgonine and benzoic acid, and some presented evidence of adulteration with aluminum sulfate and sodium carbonate. Raman spectroscopy is better than FT-IR for identifying benzoic acid and inorganic adulterants in cocaine. PMID:25428273

  16. Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy

    PubMed Central

    Wang, Dongxing; Zhu, Wenqi; Best, Michael D.; Camden, Jon P.; Crozier, Kenneth B.

    2013-01-01

    The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures (“metasurfaces”) can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent. PMID:24091825

  17. Study of exploding Al wire plasmas using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Pikuz, Sergey A.; Shelkovenko, Tatiana A.; Hoyt, Cad L.; Cahill, Adam D.; Hammer, David A.

    2012-10-01

    X-ray absorption spectroscopy is a powerful diagnostic technique useful for determining the charge state, temperature and density of plasmas under a wide range of conditions and situations. Our particular interest was the study of the core-corona system generated in electrically exploded wires and wire array Z-pinches. Two wide-bandwidth spectrographs with flat and concave cylindrically bent KAP crystals, and high-resolution spectrographs with spherically bent quartz crystals have been used on the XP and COBRA pulsers at Cornell University. The hybrid X-pinch was used as the continuum x-ray source in the photon energy range of interest for absorption spectroscopy with exploding Al wire experiments. This source is capable of producing broadband continuum x-ray pulses with micron source size and 100 ps duration. Absorption spectra of single exploded Al wires and 2 - 4 wire arrays were recorded with high spatial resolution. The parameters of the dense wire core plasmas and the ablating plasma streams were estimated under different experimental conditions. New spectral features in absorption spectra were observed.

  18. Simple fully reflective method of scatter reduction in 2D-IR spectroscopy.

    PubMed

    Spector, Ivan C; Olson, Courtney M; Huber, Christopher J; Massari, Aaron M

    2015-04-15

    A fully reflective two-dimensional IR (2D-IR) setup is described that enables efficient cancellation of scattered light from multiple pulses in the phase-matched direction. The local oscillator pulse and the pulse that stimulates the vibrational echo signal are synchronously modulated (or fibrillated) in time maintaining their phase relationships with the echo wavepacket. The modification is cost-effective and can be easily implemented on existing 2D-IR instruments, and it avoids the addition of dispersive elements into the beam paths. The fibrillation results in a decrease of waiting-time resolution of only tens of femtoseconds and has no impact on the spectral lineshape, making it a general improvement for 2D-IR spectrometers even for weakly or non-scattering samples. PMID:25872090

  19. Applications of 2D IR spectroscopy to peptides, proteins, and hydrogen-bond dynamics

    PubMed Central

    Kim, Yung Sam; Hochstrasser, Robin M.

    2010-01-01

    Following a survey of 2D IR principles this Feature Article describes recent experiments on the hydrogen-bond dynamics of small ions, amide-I modes, nitrile probes, peptides, reverse transcriptase inhibitors, and amyloid fibrils. PMID:19351162

  20. Rate constant of exciton quenching of Ir(ppy)3 with hole measured by time-resolved luminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Oyama, Shiho; Sakai, Heisuke; Murata, Hideyuki

    2016-03-01

    We observed the quenching of tris(2-phenylpyridinato)iridium(III) [Ir(ppy)3] excitons by polarons (holes or electrons) by time-resolved photoluminescence (PL) spectroscopy to clarify the dynamics of the triplet-polaron quenching of excitons. We employed a hole-only device (HOD) and an electron-only device (EOD), where the emitting layer consists of Ir(ppy)3 doped in 4,4‧-bis(carbazol-9-yl)biphenyl. Time-resolved PL spectroscopy of the EOD and HOD were measured under a constant current density. The results showed that the excitons of Ir(ppy)3 were significantly quenched only by holes. The PL decay curves of HOD were well fitted by the biexponential function, where lifetimes (τ1 and τ2) remain unchanged but the coefficient of each exponential term depends on hole current density. From the results, we proposed a model of exciton quenching where the exciton-hole quenching area expands with increasing hole current density. On the basis of the model, the triplet-polaron quenching rate constant Kq was determined.

  1. Metabolic responses of eukaryotic microalgae to environmental stress limit the ability of FT-IR spectroscopy for species identification

    PubMed Central

    Driver, Thomas; Bajhaiya, Amit K.; Allwood, J. William; Goodacre, Royston; Pittman, Jon K.; Dean, Andrew P.

    2015-01-01

    Fourier Transform Infrared (FT-IR) spectroscopy is a robust method for macromolecular analysis and differentiation of microorganisms. However, most studies are performed in controlled conditions and it is unclear whether this tool is appropriate for the identification of eukaryotic microalgae species from variable environments. In order to address this, nine closely-related species of marine and freshwater microalgae were grown under controlled (non-stressed) and variable (non-stressed and stressed) conditions, including nutrient-stressed and wastewater-stressed conditions. Following optimization of data processing methods, FT-IR spectra from all species and conditions were compared. The substantial metabolic changes that were caused by nutrient starvation restricted the ability of FT-IR spectroscopy to differentiate the microalgal species grown under variable conditions efficiently. Comparison of unsupervised and supervised multivariate data analysis methods found that principal component-discriminant function analysis was able best to differentiate between some species under controlled conditions but still gave poor differentiation under variable environmental conditions. PMID:26839765

  2. Interrogating Fiber Formation Kinetics with Automated 2D-IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Strasfeld, David B.; Ling, Yun L.; Shim, Sang-Hee; Zanni, Martin T.

    A new method for collecting 2D-IR spectra that utilizes both a pump-probe beam geometry and a mid-IR pulse shaper is used to gain a fuller understanding of fiber formation in the human islet amyloid polypeptide (hIAPP). We extract structural kinetics in order to better understand aggregation in hIAPP, the protein component of the amyloid fibers found to inhibit insulin production in type II diabetes patients.

  3. Development of a Tunable Ultra-Broadband Mid IR Pulsed Source for Nonlinear Spectroscopy

    NASA Astrophysics Data System (ADS)

    Cheng, Mark; Reynolds, Anthony; Widgren, Heather; Khalil, Munira

    2012-02-01

    We generate ultra- broadband mid-IR pulses tunable from 2.5 -- 8 μm by focusing 800 nm/400 nm pulses into various gas media. The input 800 nm light is doubled to 400 nm in a type I BBO crystal. The two orthogonally polarized φ/2φ pulses encounter a birefringent calcite crystal for time delay compensation and are subsequently focused in various gas media (air, argon, neon and nitrogen) contained within a 1.2 m gas cell using a 1 m focal length silver mirror. The tunability of the broadband mid-IR pulses arises from different gases, pressure of gases and the amount of incident 800 nm/400 nm light focused into the gas cell at a given pressure. We measure IR energies as high as 0.5 μJ/pulse for an input 800 nm energy of 3 mJ/pulse in 900 Torr of Argon. The mid IR pulses exhibit ˜2% long term stability. The ultrabroadband IR pulses have a spectral bandwidth of ˜2000 cm-1 corresponding to a sub-cycle pulse centered at 4.5 μm. We will present our preliminary efforts on using the ultrabroadband IR pulses in nonlinear experiments. The broad spectral content of this novel source affords the possibility of probing multiple vibrations in a coherent manner.

  4. Synthesis and selective IR absorption properties of iminodiacetic-acid intercalated MgAl-layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Wang, Lijing; Xu, Xiangyu; Evans, David G.; Duan, Xue; Li, Dianqing

    2010-05-01

    An MgAl-NO 3-layered double hydroxide (LDH) precursor has been prepared by a method involving separate nucleation and aging steps (SNAS). Reaction with iminodiacetic acid (IDA) under weakly acidic conditions led to the replacement of the interlayer nitrate anions by iminodiacetic acid anions. The product was characterized by XRD, FT-IR, TG-DTA, ICP, elemental analysis and SEM. The results show that the original interlayer nitrate anions of LDHs precursor were replaced by iminodiacetic acid anions and that the resulting intercalation product MgAl-IDA-LDH has an ordered crystalline structure. MgAl-IDA-LDH was mixed with low density polyethylene (LDPE) using a masterbatch method. LDPE films filled with MgAl-IDA-LDH showed a higher mid to far infrared absorption than films filled with MgAl-CO 3-LDH in the 7-25 μm range, particularly in the key 9-11 μm range required for application in agricultural plastic films.

  5. Synthesis and selective IR absorption properties of iminodiacetic-acid intercalated MgAl-layered double hydroxide

    SciTech Connect

    Wang Lijing; Xu Xiangyu; Evans, David G.; Duan Xue; Li Dianqing

    2010-05-15

    An MgAl-NO{sub 3}-layered double hydroxide (LDH) precursor has been prepared by a method involving separate nucleation and aging steps (SNAS). Reaction with iminodiacetic acid (IDA) under weakly acidic conditions led to the replacement of the interlayer nitrate anions by iminodiacetic acid anions. The product was characterized by XRD, FT-IR, TG-DTA, ICP, elemental analysis and SEM. The results show that the original interlayer nitrate anions of LDHs precursor were replaced by iminodiacetic acid anions and that the resulting intercalation product MgAl-IDA-LDH has an ordered crystalline structure. MgAl-IDA-LDH was mixed with low density polyethylene (LDPE) using a masterbatch method. LDPE films filled with MgAl-IDA-LDH showed a higher mid to far infrared absorption than films filled with MgAl-CO{sub 3}-LDH in the 7-25 {mu}m range, particularly in the key 9-11 {mu}m range required for application in agricultural plastic films. - Graphical abstract: Intercalation of iminodiacetic acid (IDA) anions in a MgAl-NO{sub 3}-layered double hydroxide host leads to an enhancement of its infrared absorbing ability for application in agricultural plastic films.

  6. Monitoring the folding kinetics of a β-hairpin by time-resolved IR spectroscopy in silico.

    PubMed

    Daidone, Isabella; Thukral, Lipi; Smith, Jeremy C; Amadei, Andrea

    2015-04-01

    Protein folding is one of the most fundamental problems in modern biochemistry. Time-resolved infrared (IR) spectroscopy in the amide I region is commonly used to monitor folding kinetics. However, associated atomic detail information on the folding mechanism requires simulations. In atomistic simulations structural order parameters are typically used to follow the folding process along the simulated trajectories. However, a rigorous test of the reliability of the mechanisms found in the simulations requires calculation of the time-dependent experimental observable, i.e., in the present case the IR signal in the amide I region. Here, we combine molecular dynamics simulation with a mixed quantum mechanics/molecular mechanics theoretical methodology, the Perturbed Matrix Method, in order to characterize the folding of a β-hairpin peptide, through modeling the time-dependence of the amide I IR signal. The kinetic and thermodynamic data (folding and unfolding rate constants, and equilibrium folded- and unfolded-state probabilities) obtained from the fit of the calculated signal are in good agreement with the available experimental data [Xu et al. J. Am. Chem. Soc. 2003, 125, 15388-15394]. To the best of our knowledge, this is the first report of the simulation of the time-resolved IR signal of a complex process occurring on a long (microsecond) time scale. PMID:25777154

  7. Intermolecular Hydrogen Bonds Formed Between Amino Acid Molecules in Aqueous Solution Investigated by Temperature-jump Nanosecond Time-resolved Transient Mid-IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ye, Man-ping; Li, Heng; Zhang, Qing-li; Weng, Yu-xiang; Qiu, Xiang-gang

    2007-08-01

    Carboxyl (COO-) vibrational modes of two amino acids histidine and glycine in D2O solution were investigated by temperature-dependent FTIR spectroscopy and temperature-jump nanosecond time-resolved IR difference absorbance spectroscopy. The results show that hydrogen bonds are formed between amino acid molecules as well as between the amino acid molecule and the solvent molecules. The asymmetric vibrational frequency of COO- around 1600-1610 cm-1 is blue shifted when raising temperature, indicating that the strength of the hydrogen bonds becomes weaker at higher temperature. Two bleaching peaks at 1604 and 1612 cm-1 were observed for histidine in response to a temperature jump from 10 °C to 20 °C. The lower vibrational frequency at 1604 cm-1 is assigned to the chain COO- group which forms the intermolecular hydrogen bond with NH3+ group, while the higher frequency at 1612 cm-1 is assigned to the end COO- group forming hydrogen bonds with the solvent molecules. This is because that the hydrogen bonds in the former are expected to be stronger than the latter. In addition the intensities of these two bleaching peaks are almost the same. In contrast, only the lower frequency at 1604 cm-1 bleaching peak has been observed for glycine. The fact indicates that histidine molecules form a dimer-like intermolecular chain while glycine forms a relatively longer chain in the solution. The rising phase of the IR absorption kinetics in response to the temperature-jump detected at 1604 cm-1 for histidine is about 30+/-10 ns, within the resolution limit of our instrument, indicating that breaking or weakening the hydrogen bond is a very fast process.

  8. Mid-IR, Far-IR, Raman micro-spectroscopy, and FESEM-EDX study of IDP L2021C5: Clues to its origin

    NASA Astrophysics Data System (ADS)

    Brunetto, R.; Borg, J.; Dartois, E.; Rietmeijer, F. J. M.; Grossemy, F.; Sandt, C.; Le Sergeant d'Hendecourt, L.; Rotundi, A.; Dumas, P.; Djouadi, Z.; Jamme, F.

    2011-04-01

    Interplanetary Dust Particles (IDPs) are potentially of cometary origin. They may therefore provide important clues to a better understanding of the early Solar System physical and chemical conditions. A chondritic porous aggregate IDP (named L2021C5) was analyzed using mid to far FTIR (2-60 μm) micro-spectroscopy, Raman micro-spectroscopy, field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) analyses. The IDP was pressed between diamond windows to increase the quality of the spectral data by overcoming the diffraction limitation and minimizing light scattering effects from particles of a global size similar to the wavelength of the observation. This combination of techniques has enabled a mineralogical, organic and compositional description of the compressed particle. The IR spectra show that in L2021C5 amorphous silicates are more abundant than crystalline ones, and that the crystalline component is richer in olivine than in pyroxene. The composition and distribution of these inorganic components match very well the small silicate grains emission observed for comet Hale-Bopp from ISO-SWS spectra. Raman spectroscopy has allowed the detection of carbonaceous structures displaying different degrees of order, covering almost the whole range observed so far for IDPs. The combination of the three analytical techniques indicates that L2021C5 is a low-Ca, chondritic porous aggregate that experienced only mild flash heating on atmospheric entry, as indicated by the disordered carbon properties, the Fe/S atomic ratio of sulfides, the absence of Na depletion, and the small depletion of S. Based on a plausible cometary origin and on the estimated low entry velocity, we suggest that this IDP came from the Zodiacal cloud that is dominated by dust from Jupiter-Family comets.

  9. Theory of dynamic absorption spectroscopy of nonstationary states. 4. Application to 12-fs resonant impulsive Raman spectroscopy of bacteriorhodopsin

    SciTech Connect

    Pollard, W.T.; Peteanu, L.A.; Mathies, R.A.

    1992-07-23

    A time-dependent theory for femtosecond dynamic absorption spectroscopy is used to describe the creation and observation of molecular ground-state vibrational coherence through the resonance impulsive stimulated Raman mechanism. Model calculations show that the oscillatory absorption signal that arises from this ground-state coherence is maximized for a limited range of pulse lengths and that there is a complex relationship between the probe wavelength and the strength of the spectral oscillations. The generalized time-dependent linear susceptibility of the nonstationary system created by the impulsive pump pulse is defined and used to discuss the strong dependence of the measured signals on the properties of the probe pulse. Finally, calculations are presented to analyze the high-frequency oscillations ({approximately}20-fs period) recently observed in the transient absorption spectra of light-adapted bacteriorhodopsin (BR{sub 568}) following excitation with a 12-fs optical pulse. At the probe wavelengths used in this experiment, the contribution of stimulated emission is negligible at long times because of the extremely rapid excited-state isomerization; as a result, the spectral oscillations observed after this time are due to the impulsive excitation of coherent vibrations in the ground state. The transient response observed for BR{sub 568} is calculated using a 29-mode harmonic potential surface derived from a prior resonance Raman intensity analysis. Both the oscillatory signals and their dependence on the probe wavelength are satisfactorily reproduced. 68 refs., 11 figs.

  10. Absorption spectroscopy of three-dimensional bacteriorhodopsin crystals at cryogenic temperatures: effects of altered hydration.

    PubMed

    Portuondo-Campa, E; Schenkl, S; Dolder, M; Chergui, M; Landau, E M; Haacke, S

    2006-04-01

    A comparative study of absorption spectroscopy at 100 K has been performed on three-dimensional crystals of bacteriorhodopsin extracted from a lipidic cubic phase and on native purple membrane. A modified microspectrophotometer has been designed which yields absorption data with a high signal-to-noise ratio and remarkable reproducibility. Excellent agreement of the absorption spectra of the three-dimensional crystals and the purple membrane is observed provided that a rigorous crystal-handling procedure is followed. This result supports the equivalence of the protein structure in both the cubic phase crystals and the native purple membrane. On the other hand, it is shown that dramatic deviations of the crystal spectrum can be induced by minor changes in the extraction method. Exposure to air at room temperature can lead within a short time to an irreversible dehydration manifested by a distinct species with an absorption maximum at 500 nm. Exposure of the crystals to a buffer with lower ionic strength than the crystallization solution produces a different spectral form with an absorption maximum at 477 nm, which was assigned to a distorted protein conformation induced by osmotic stress. The extreme sensitivity of these crystals to experimental conditions is relevant for X-ray structural studies, in particular as different experimental treatments are implemented to trap the intermediates of the protein's photocycle. PMID:16552137

  11. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy

    SciTech Connect

    Hager, J. D. Lanier, N. E.; Kline, J. L.; Flippo, K. A.; Bruns, H. C.; Schneider, M.; Saculla, M.; McCarville, T.

    2014-11-15

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO{sub 2} foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured.

  12. [Study on removing the lamp spectrum structure in differential optical absorption spectroscopy].

    PubMed

    Qu, Xiao-ying; Li, Yu-jin

    2010-11-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range, and nowadays this technique has been widely utilized to measure trace polluted gases in the atmosphere e.g. SO2, NO2, O3, HCHO, etc. However, there exists lamp (xenon lamp or deuteriumlamp) spectrum structure in the measured band (300-700 nm) of the absorption spectra of atmosphere, which badly impacts on precision of retrieving the concentration of trace gases in the atmosphere. People home and abroad generally employ two ways to handle this problem, one is segmenting band retrieving method, another is remedial retrieving method. In the present paper, a new retrieving method to deal with this trouble is introduced. The authors used moving-window average smoothing method to obtain the slow part of the absorption spectra of atmosphere, then achieved the lamp (xenon lamp in the paper) spectrum structure in the measured band of the absorption spectra of atmosphere. The authors analyzed and retrieved the measured spectrum of the atmosphere, and the result is better than the forenamed ways. Chi-square of residuum is 2.995 x 10(-4), and this method was proved to be able to avoid shortcoming of choosing narrowband and disadvantage of discovering the new component of atmosphere in retrieving the concentration of air pollutants and measuring the air pollutants. PMID:21284148

  13. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy.

    PubMed

    Hager, J D; Lanier, N E; Kline, J L; Flippo, K A; Bruns, H C; Schneider, M; Saculla, M; McCarville, T

    2014-11-01

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO2 foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured. PMID:25430177

  14. Distribution of Hydroxyl Groups in Kukersite Shale Oil: Quantitative Determination Using Fourier Transform Infrared (FT-IR) Spectroscopy.

    PubMed

    Baird, Zachariah Steven; Oja, Vahur; Järvik, Oliver

    2015-05-01

    This article describes the use of Fourier transform infrared (FT-IR) spectroscopy to quantitatively measure the hydroxyl concentrations among narrow boiling shale oil cuts. Shale oil samples were from an industrial solid heat carrier retort. Reference values were measured by titration and were used to create a partial least squares regression model from FT-IR data. The model had a root mean squared error (RMSE) of 0.44 wt% OH. This method was then used to study the distribution of hydroxyl groups among more than 100 shale oil cuts, which showed that hydroxyl content increased with the average boiling point of the cut up to about 350 °C and then leveled off and decreased. PMID:25811170

  15. Non-destructive and in situ identification of rice paper, seals and pigments by FT-IR and XRD spectroscopy.

    PubMed

    Na, Na; Ouyang, Qi-Ming; Ma, Hui; Ouyang, Jin; Li, Yanping

    2004-11-15

    This paper studied the chemical characteristics of rice paper, pigments and seals on Chinese calligraphies and traditional Chinese paintings. The techniques used here were Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD). FT-IR allows good identification of the substances present in pigments and inkpads and differentiates each era of rice paper. This can be the base of estimating the age of rice paper. Different crystalline phases can be identified by XRD, which is further evidence to separate different kinds of pigments or inkpads. Both of these methods were non-destructive in situ analysis and can be used in the identification in calligraphies and traditional Chinese paintings. These results confirmed that the applied techniques are relatively quicker and more reliable than traditional approaches authenticated by years of experience. PMID:18969703

  16. Dynamics of phonons in Sr3Ir4Sn13: an experimental study by ultrafast spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Luo, C. W.; Cheng, P. C.; Tu, C. M.; Kuo, C. N.; Wang, C. M.; Lue, C. S.

    2016-07-01

    We report a study of ultrafast dynamics of photoexcited electrons and phonons in Sr3Ir4Sn13 using dual-color transient reflectivity change ({{Δ }}R/R) measurements. Time resolved optical spectroscopy of collective excitations reveal the marked features near its structural phase transition temperature {T}* ≃ 147 K. Two distinctive oscillatory timescales in {{Δ }}R/R have been clearly resolved. The rapid THz-range oscillations are attributed to the dynamics of the optical phonons which strongly correlate to the structural phase transition. The slow GHz-range oscillatory phenomenon which only occurs below about 150 K is associated with the dynamic response of the longitudinal-acoustic phonons. These low-energy phonons show a softening feature on approaching the transition temperature, also indicating a strong relevance to the structural phase transition. The information that we demonstrated would provide a deeper understanding of the structural phase transition in Sr3Ir4Sn13.

  17. Far-ir Pah Spectroscopy And The Identification Of An Individual Astronomical Pah Molecule

    NASA Astrophysics Data System (ADS)

    Boersma, Christiaan; Allamandola, L. J.; Bauschlicher, C. W.; Ricca, A.; Mattioda, A. L.; Hudgins, D.; Cami, J.; Peeters, E.; Sánchez de Armas, F.; Puerta Saborido, G.

    2010-05-01

    Polycyclic Aromatic Hydrocarbons (PAHs) are widespread across the Universe and influence many stages of the Galactic lifecycle. The presence of PAHs has been well established and the rich mid-IR PAH spectrum is now commonly used as a probe into inter(stellar) environments. With a new spectral window opening up in the far-IR, the quest for identifying a unique member of the interstellar PAH family has begun. To guide this search, the far-IR (> 20 μm) spectra of different sets of PAHs are investigated using the NASA Ames PAH IR Spectroscopic Database - a large coherent set (> 600 spectra) of laboratory measured and DFT computed infrared spectra of PAHs from C10H8 to C130H28. These sets explore the influence of size, shape, charge and composition on the far-IR PAH spectrum. The far-IR is the domain of the so- called `drumhead’ modes and other molecular vibrations involving low order bending vibrations of the carbon skeleton as a whole. As for drums, these modes are considered to be very molecule and shape specific and promise to be a key diagnostic for specific PAHs. Here, the sensitivity of these `drumhead’ modes to size and shape is assessed by comparing the frequencies of the lowest drumhead modes of a family of circular shaped (the coronene `family') and rhombus shaped (the pyrene `family') PAH molecules. From the study of the far-IR PAH spectra of different sets as well as from the analysis of the `drumhead’ modes, some suggestions for an observing strategy are made.

  18. Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kramer, Patrick L.; Nishida, Jun; Giammanco, Chiara H.; Tamimi, Amr; Fayer, Michael D.

    2015-05-01

    In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, , than in the standard all parallel configuration, , in which all four pulses have the same polarization. The 2D IR experiment with polarizations ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system.

  19. Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy.

    PubMed

    Kramer, Patrick L; Nishida, Jun; Giammanco, Chiara H; Tamimi, Amr; Fayer, Michael D

    2015-05-14

    In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, 〈XXY Y〉, than in the standard all parallel configuration, 〈XXXX〉, in which all four pulses have the same polarization. The 2D IR experiment with polarizations 〈XY XY〉 ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the 〈XXXX〉 configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system. PMID:25978898

  20. Cavity Enhanced Absorption Spectroscopy with a red LED source for NOx trace analysis

    NASA Astrophysics Data System (ADS)

    Ventrillard Courtillot, I.; Sciamma O'Brien, E.; Méjean, G.; Romanini, D.

    2009-04-01

    This study presents a high sensitivity absorption system using a red LED source emitting at 625 nm and a small CCD spectrometer as detector [1]. This system is based on IBB-CEAS (Incoherent Broad Band Cavity Enhanced Absorption Spectroscopy). The expected application is the measurement of NO2 and NO3 in urban concentration (ppbv and ppmv levels). The IBB-CEAS was firstly developed with arc lamps and then with LED. Systems based on this technique are easy to use, highly sensitive, compact and robust. They also are inexpensive. Existent techniques to measure NO2 and NO3 are generally slow or not sensitive enough and need frequently calibrations (chemical luminescent) or are characterized by a low spatial resolution (Long Path Differential Optical Absorption Spectroscopy). Previous works based on diodes lasers emitting around 410 nm and coupled with High Finess Cavity proved a highest sensibility than ppbv and a time measurement of 0.1 s [2]. This sensibility is necessary for measurements in unpolluted environment but a more expensive and more complex system is needed. NO2 is chosen for testing as it is stable and available in calibrated diluted samples. An excellent agreement in the range from 610 nm to 630 nm was gotten between an absorption spectrum obtained by IBB-CEAS and a spectrum calculated using a reference NO2 absorption cross section by Voigt et al [3] (after convolution with a 2.05-nm FWHM Gaussian simulating our spectrometer response function). The reflectivity of the mirrors was determined with a commercial spectrophotometer and was used to deduce the absorption spectrum of NO2 from the transmission spectrum of the cavity. We obtained by estimating the sensitivity of our setup from the noise in a baseline measurement of absorption, (standard deviation = 2E-10 cm-1). This corresponds (under atmospheric conditions) to a sensitivity about 0.5 ppbv. NO3 cross-section absorption is 600 times higher than the NO2 (at 623 nm), so a detection limit of 1 pptv is

  1. Cavity ring-down spectroscopy (CRDS) system for measuring atmospheric mercury using differential absorption

    NASA Astrophysics Data System (ADS)

    Pierce, A.; Obrist, D.; Moosmuller, H.; Moore, C.

    2012-04-01

    Atmospheric elemental mercury (Hg0) is a globally pervasive element that can be transported and deposited to remote ecosystems where it poses — particularly in its methylated form — harm to many organisms including humans. Current techniques for measurement of atmospheric Hg0 require several liters of sample air and several minutes for each analysis. Fast-response (i.e., 1 second or faster) measurements would improve our ability to understand and track chemical cycling of mercury in the atmosphere, including high frequency Hg0 fluctuations, sources and sinks, and chemical transformation processes. We present theory, design, challenges, and current results of our new prototype sensor based on cavity ring-down spectroscopy (CRDS) for fast-response measurement of Hg0 mass concentrations. CRDS is a direct absorption technique that implements path-lengths of multiple kilometers in a compact absorption cell using high-reflectivity mirrors, thereby improving sensitivity and reducing sample volume compared to conventional absorption spectroscopy. Our sensor includes a frequency-doubled, dye-laser emitting laser pulses tunable from 215 to 280 nm, pumped by a Q-switched, frequency tripled Nd:YAG laser with a pulse repetition rate of 50 Hz. We present how we successfully perform automated wavelength locking and stabilization of the laser to the peak Hg0 absorption line at 253.65 nm using an external isotopically-enriched mercury (202Hg0) cell. An emphasis of this presentation will be on the implementation of differential absorption measurement whereby measurements are alternated between the peak Hg0 absorption wavelength and a nearby wavelength "off" the absorption line. This can be achieved using a piezo electric tuning element that allows for pulse-by-pulse tuning and detuning of the laser "online" and "offline" of the Hg absorption line, and thereby allows for continuous correction of baseline extinction losses. Unexpected challenges with this approach included

  2. An experimental set-up to apply polarization modulation to infrared reflection absorption spectroscopy for improved in situ studies of atmospheric corrosion processes

    SciTech Connect

    Wiesinger, R.; Schade, U.; Kleber, Ch.; Schreiner, M.

    2014-06-15

    A new set-up for improved monitoring of atmospheric corrosion processes in situ and in real-time is presented. To characterize chemical structures of thin films on metal surfaces surface sensitive analytical techniques are required. One possible technique is Infrared Reflection Absorption Spectroscopy (IRRAS) which has become an established method to investigate surface corrosion films of thicknesses less than 200 nm. However, there are limitations related to the sensitivity of these measurements, in case of investigating ultrathin films or absorption bands of interest, surface species are superimposed by atmospheric background absorption, which changes during in situ measurements in ambient atmospheres. These difficulties of in situ surface reflection measurements can be eliminated by availing the polarization selectivity of adsorbed surface species. At grazing angles of incidence the absorption of p-polarized infrared radiation by thin surface films on metals is enhanced, while the absorption of s-polarized light by this film is nearly zero. This different behavior of the polarization properties leads to strong selection rules at the surface and can therefore be used to identify molecules adsorbed on metal surfaces. Polarization Modulation (PM) of the infrared (IR) light takes advantage of this disparity of polarization on sample surfaces and in combination with IRRAS yielding a very sensitive and surface-selective method for obtaining IR spectra of ultra-thin films on metal surfaces. An already existing in situ IRRAS/Quartz Crystal Microbalance weathering cell was combined with PM and evaluated according to its applicability to study in situ atmospheric corrosion processes. First real-time measurements on silver samples exposed to different atmospheres were performed showing the advantage of PM-IRRAS compared to conventional IRRAS for such investigations.

  3. An experimental set-up to apply polarization modulation to infrared reflection absorption spectroscopy for improved in situ studies of atmospheric corrosion processes.

    PubMed

    Wiesinger, R; Schade, U; Kleber, Ch; Schreiner, M

    2014-06-01

    A new set-up for improved monitoring of atmospheric corrosion processes in situ and in real-time is presented. To characterize chemical structures of thin films on metal surfaces surface sensitive analytical techniques are required. One possible technique is Infrared Reflection Absorption Spectroscopy (IRRAS) which has become an established method to investigate surface corrosion films of thicknesses less than 200 nm. However, there are limitations related to the sensitivity of these measurements, in case of investigating ultrathin films or absorption bands of interest, surface species are superimposed by atmospheric background absorption, which changes during in situ measurements in ambient atmospheres. These difficulties of in situ surface reflection measurements can be eliminated by availing the polarization selectivity of adsorbed surface species. At grazing angles of incidence the absorption of p-polarized infrared radiation by thin surface films on metals is enhanced, while the absorption of s-polarized light by this film is nearly zero. This different behavior of the polarization properties leads to strong selection rules at the surface and can therefore be used to identify molecules adsorbed on metal surfaces. Polarization Modulation (PM) of the infrared (IR) light takes advantage of this disparity of polarization on sample surfaces and in combination with IRRAS yielding a very sensitive and surface-selective method for obtaining IR spectra of ultra-thin films on metal surfaces. An already existing in situ IRRAS/Quartz Crystal Microbalance weathering cell was combined with PM and evaluated according to its applicability to study in situ atmospheric corrosion processes. First real-time measurements on silver samples exposed to different atmospheres were performed showing the advantage of PM-IRRAS compared to conventional IRRAS for such investigations. PMID:24985826

  4. An experimental set-up to apply polarization modulation to infrared reflection absorption spectroscopy for improved in situ studies of atmospheric corrosion processes

    NASA Astrophysics Data System (ADS)

    Wiesinger, R.; Schade, U.; Kleber, Ch.; Schreiner, M.

    2014-06-01

    A new set-up for improved monitoring of atmospheric corrosion processes in situ and in real-time is presented. To characterize chemical structures of thin films on metal surfaces surface sensitive analytical techniques are required. One possible technique is Infrared Reflection Absorption Spectroscopy (IRRAS) which has become an established method to investigate surface corrosion films of thicknesses less than 200 nm. However, there are limitations related to the sensitivity of these measurements, in case of investigating ultrathin films or absorption bands of interest, surface species are superimposed by atmospheric background absorption, which changes during in situ measurements in ambient atmospheres. These difficulties of in situ surface reflection measurements can be eliminated by availing the polarization selectivity of adsorbed surface species. At grazing angles of incidence the absorption of p-polarized infrared radiation by thin surface films on metals is enhanced, while the absorption of s-polarized light by this film is nearly zero. This different behavior of the polarization properties leads to strong selection rules at the surface and can therefore be used to identify molecules adsorbed on metal surfaces. Polarization Modulation (PM) of the infrared (IR) light takes advantage of this disparity of polarization on sample surfaces and in combination with IRRAS yielding a very sensitive and surface-selective method for obtaining IR spectra of ultra-thin films on metal surfaces. An already existing in situ IRRAS/Quartz Crystal Microbalance weathering cell was combined with PM and evaluated according to its applicability to study in situ atmospheric corrosion processes. First real-time measurements on silver samples exposed to different atmospheres were performed showing the advantage of PM-IRRAS compared to conventional IRRAS for such investigations.

  5. Conformational Analysis of R-(+)-3-METHYLCYCLOPENTANONE by IR Spectroscopy in Para-Hydrogen Crystal

    NASA Astrophysics Data System (ADS)

    Al-Basheer, Watheq; Toh, Shin Yi; Miyazaki, Jun; Momose, Takamasa

    2014-06-01

    Para-hydrogen (pH_2) soft quantum crystal is an ideal isolation matrix due to its impressive intrinsic properties, i.e. its significant lattice constant, large zero-point vibration as well as its ability to repair itself of crystal defects. To investigate molecular conformation of a chiral ketone, IR spectra of R-(+)-3-methylcyclopentanone (R3MCP), hosted in pH_2 crystal, were recorded as a function of sample concentration and host pH_2 crystal temperature over the low deposition range {3.5-6.0K}. IR spectra of R3MCP in pH_2 crystal will be presented and compared against corresponding spectra in Ar matrix as well as IR spectra of the neat crystalline R3MCP at low deposition temperatures. Furthermore, density functional theory calculations of simulated IR spectra for the optimized geometries of R3MCP, equatorial-methyl and axial-methyl conformers are compared against experimental spectra for the purpose of investigating molecular conformation. Upon comparison between theoretical and experimental IR spectra, vibrational modes arising from equatorial and axial conformers have been successfully assigned and related to the individual conformer's structure.

  6. Triosmium clusters on a support: determination of structure by X-ray absorption spectroscopy and high-resolution microscopy.

    PubMed

    Mehraeen, Shareghe; Kulkarni, Apoorva; Chi, Miaofang; Reed, Bryan W; Okamoto, Norihiko L; Browning, Nigel D; Gates, Bruce C

    2011-01-17

    The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os(3) (CO)(12) ] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03±0.06 Å. The EXAFS OsOs coordination number of 2.1±0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02±0.04 Å. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80±0.14 Å, matching the EXAFS value of 2.89±0.06 Å. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters. PMID:21226118

  7. Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

    SciTech Connect

    Shareghe, Mehraeen; Chi, Miaofang; Browning, Nigel D.

    2011-01-01

    The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os{sub 3}(CO){sub 12}] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03 {+-} 0.06 {angstrom}. The EXAFS OsOs coordination number of 2.1 {+-} 0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02 {+-} 0.04 {angstrom}. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80 {+-} 0.14 {angstrom}, matching the EXAFS value of 2.89 {+-} 0.06 {angstrom}. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters.

  8. Surface Arsenic Speciation of a Drinking-Water Treatment Residual Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Makris, K.C.; Sarkar, D.; Parsons, J.G.; Datta, R.; Gardea-Torresdey, J.L.

    2009-06-03

    Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing <90% of the initial added As (15,000 mg kg{sup -1}) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg{sup -1}) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.

  9. High-performance dispersive Raman and absorption spectroscopy as tools for drug identification

    NASA Astrophysics Data System (ADS)

    Pawluczyk, Olga; Andrey, Sam; Nogas, Paul; Roy, Andrew; Pawluczyk, Romuald

    2009-02-01

    Due to increasing availability of pharmaceuticals from many sources, a need is growing to quickly and efficiently analyze substances in terms of the consistency and accuracy of their chemical composition. Differences in chemical composition occur at very low concentrations, so that highly sensitive analytical methods become crucial. Recent progress in dispersive spectroscopy with the use of 2-dimensional detector arrays, permits for signal integration along a long (up to 12 mm long) entrance slit of a spectrometer, thereby increasing signal to noise ratio and improving the ability to detect small concentration changes. This is achieved with a non-scanning, non-destructive system. Two different methods using P&P Optica high performance spectrometers were used. High performance optical dispersion Raman and high performance optical absorption spectroscopy were employed to differentiate various acetaminophen-containing drugs, such as Tylenol and other generic brands, which differ in their ingredients. A 785 nm excitation wavelength was used in Raman measurements and strong Raman signals were observed in the spectral range 300-1800 cm-1. Measurements with the absorption spectrometer were performed in the wavelength range 620-1020 nm. Both Raman and absorption techniques used transmission light spectrometers with volume phase holographic gratings and provided sufficient spectral differences, often structural, allowing for drug differentiation.

  10. Electronic relaxation dynamics of PCDA-PDA studied by transient absorption spectroscopy.

    PubMed

    Joung, Joonyoung F; Baek, Junwoo; Kim, Youngseo; Lee, Songyi; Kim, Myung Hwa; Yoon, Juyoung; Park, Sungnam

    2016-08-17

    Photo-curable polymers originating from 10,12-pentacosadiynoic acid (PCDA-PDA) are commonly used polydiacetylenes (PDAs). PCDA-PDA exhibits thermochromic properties undergoing a unique colorimetric transition from blue to red as the temperature is increased from low to high. In this work, we have carefully studied the temperature-dependent optical properties of PCDA-PDA by using UV-visible absorption, FTIR, Raman, and transient absorption (TA) spectroscopy in combination with quantum chemical calculations. Temperature-dependent UV-visible absorption spectra indicate that PCDA-PDA exhibits reversible thermochromic properties up to 60 °C and its thermochromic properties become irreversible above 60 °C. Such distinct thermochromic properties are also manifested in TA signals so that the electronically excited PCDA-PDA relaxes to the ground state via an intermediate state at 20 °C (blue form) but it relaxes directly back to the ground state at 80 °C (red form). The electronic relaxation dynamics of PCDA-PDA are comprehensively analyzed based on different kinetic models by using the global fitting analysis method. The intermediate state in the blue form of PCDA-PDA is clearly found to be responsible for fluorescence quenching. FTIR and Raman spectroscopy and quantum chemical calculations confirm that the H-bonds between the carboxylic acid groups in PCDA-PDA are broken at high temperatures leading to an irreversible structural change of PCDA-PDA. PMID:27492212

  11. Femtosecond x-ray absorption spectroscopy with hard x-ray free electron laser

    SciTech Connect

    Katayama, Tetsuo; Togashi, Tadashi; Tono, Kensuke; Kameshima, Takashi; Inubushi, Yuichi; Sato, Takahiro; Hatsui, Takaki; Yabashi, Makina; Obara, Yuki; Misawa, Kazuhiko; Bhattacharya, Atanu; Kurahashi, Naoya; Ogi, Yoshihiro; Suzuki, Toshinori

    2013-09-23

    We have developed a method of dispersive x-ray absorption spectroscopy with a hard x-ray free electron laser (XFEL), generated by a self-amplified spontaneous emission (SASE) mechanism. A transmission grating was utilized for splitting SASE-XFEL light, which has a relatively large bandwidth (ΔE/E ∼ 5 × 10{sup −3}), into several branches. Two primary split beams were introduced into a dispersive spectrometer for measuring signal and reference spectra simultaneously. After normalization, we obtained a Zn K-edge absorption spectrum with a photon-energy range of 210 eV, which is in excellent agreement with that measured by a conventional wavelength-scanning method. From the analysis of the difference spectra, the noise ratio was evaluated to be ∼3 × 10{sup −3}, which is sufficiently small to trace minute changes in transient spectra induced by an ultrafast optical laser. This scheme enables us to perform single-shot, high-accuracy x-ray absorption spectroscopy with femtosecond time resolution.

  12. Rapid characterisation of archaeological midden components using FT-IR spectroscopy, SEM-EDX and micro-XRD

    NASA Astrophysics Data System (ADS)

    Shillito, Lisa-Marie; Almond, Matthew J.; Nicholson, James; Pantos, Manolis; Matthews, Wendy

    2009-07-01

    Samples taken from middens at the Neolithic site of Çatalhöyük in Turkey have been analysed using IR spectroscopy backed up by powder XRD and SEM-EDX. Microcomponents studied include fossil hackberries (providing evidence of ancient diet and seasonality), mineral nodules (providing evidence of post-depositional change) and phytoliths (mineralised plant cells, providing evidence of usage of plant species). Finely laminated ashy deposits have also been investigated allowing chemical and mineralogical variations to be explored. It is found that many layers which appear visually to be quite distinctive have, in fact, very similar mineralogy.

  13. Fourier transform two-dimensional electronic-vibrational spectroscopy using an octave-spanning mid-IR probe.

    PubMed

    Gaynor, James D; Courtney, Trevor L; Balasubramanian, Madhumitha; Khalil, Munira

    2016-06-15

    The development of coherent Fourier transform two-dimensional electronic-vibrational (2D EV) spectroscopy with acousto-optic pulse-shaper-generated near-UV pump pulses and an octave-spanning broadband mid-IR probe pulse is detailed. A 2D EV spectrum of a silicon wafer demonstrates the full experimental capability of this experiment, and a 2D EV spectrum of dissolved hexacyanoferrate establishes the viability of our 2D EV experiment for studying condensed phase molecular ensembles. PMID:27304316

  14. Complexation of Neptunium(V) with Glutaroimide Dioxime: A Study by Absorption Spectroscopy, Microcalorimetry, and Density Functional Theory Calculations.

    PubMed

    Ansari, Seraj A; Bhattacharyya, Arunasis; Zhang, Zhicheng; Rao, Linfeng

    2015-09-01

    Complexation of NpO2(+) ions with glutaroimide dioxime (H2L), a cyclic imide dioxime ligand that has been shown to form strong complexes with UO2(2+) in aqueous solutions, was studied by absorption spectroscopy and microcalorimetry in 1.0 M NaClO4 aqueous solutions. NpO2(+) forms two successive complexes, NpO2(HL)(aq) and NpO2(HL)2(-) (where HL(-) stands for the partially deprotonated glutaroimide dioxime ligand), with stability constants of log β111 = 17.8 ± 0.1 and log β122 = 33.0 ± 0.2, respectively. The complexation is both enthalpy- and entropy-driven, with negative enthalpies (ΔH111 = -52.3 ± 1.0 kJ/mol and ΔH122 = -96.1 ± 1.4 kJ/mol) and positive entropies (ΔS111 = 164 ± 3 J/mol/K and ΔS122 = 310 ± 4 J/mol/K). The thermodynamic parameters suggest that, similar to complexation of UO2(2+), the ligand coordinates with NpO2(+) in a tridentate mode, via the two oxygen atoms of the oxime groups and the nitrogen atom of the imide group. Density functional theory calculations have helped to interpret the optical absorption properties of the NpO2(HL)2(-) complex, by showing that the cis and trans configurations of the complex have very similar energies so that both configurations could be present in the aqueous solutions. It is the noncentrosymmetric cis configuration that makes the 5f → 5f transition allowable so that the NpO2(HL)2(-) complex absorbs in the near-IR region. PMID:26263050

  15. X-ray absorption spectroscopy from H-passivated porous Si and oxidized Si nanocrystals

    SciTech Connect

    Schuppler, S.; Marcus, M.A.; Friedman, S.L.

    1994-11-01

    Quantum confinement in nanoscale Si structures is widely believed to be responsible for the visible luminescence observed from anodically etched porous silicon (por-Si), but little is known about the actual size or shape of these structures. Extended x-ray absorption fine structure data from a wide variety of por-Si samples show significantly reduced average Si coordination numbers due to the sizable contribution of surface-coordinated H. (The IUSI ratios, as large as 1.2, were independently confirmed by ir-absorption and {alpha}-recoil measurements.) The Si coordinations imply very large surface/volume ratios, enabling the average Si structures to be identified as crystalline particles (not wires) whose dimensions are typically <15 {Angstrom}. Comparison of the size-dependent peak luminescence energies with those of oxidized Si nanocrystals, whose shapes are known, shows remarkable agreement. Furthermore, near-edge x-ray absorption fine structure measurements of the nanocrystals shows the outer oxide and interfacial suboxide layers to be constant over a wide range of nanocrystal sizes. The combination of these results effectively rules out surface species as being responsible for the observed visible luminescence in por-Si, and strongly supports quantum confinement as the dominant mechanism occurring in Si particles which are substantially smaller than previously reported or proposed.

  16. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-01

    Laser spectroscopy is a powerful tool for analyzing small molecules, i.e. in the gas phase. In the mid-infrared spectral region quantum cascade lasers (QCLs) have been established as the most frequently used laser radiation source. Spectroscopy of larger molecules in the gas phase, of complex mixtures, and analysis in the liquid phase requires a broader tuning range and is thus still the domain of Fourier transform infrared (FTIR) spectroscopy. However, the development of tunable external cavity (EC) QCLs is starting to change this situation. The main advantage of QCLs is their high spectral emission power that is enhanced by a factor of 10(4) compared with thermal light sources. Obviously, transmission measurements with EC-QCLs in strongly absorbing samples are feasible, which can hardly be measured by FTIR due to detector noise limitations. We show that the high power of EC-QCLs facilitates spectroscopy beyond simple absorption measurements. Starting from QCL experiments with liquid samples, we show results of fiber evanescent field analysis (FEFA) to detect pesticides in drinking water. FEFA is a special case of attenuated total reflection spectroscopy. Furthermore, powerful CW EC-QCLs enable fast vibrational circular dichroism (VCD) spectroscopy of chiral molecules in the liquid phase - a technique which is very time consuming with standard FTIR equipment. We present results obtained for the chiral compound 1,1'-bi-2-naphthol (BINOL). Finally, powerful CW EC-QCLs enable the application of laser photothermal emission spectroscopy (LPTES). We demonstrate this for a narrowband and broadband absorber in the gas phase. All three techniques have great potential for MIR process analytical applications. PMID:24367797

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

    NASA Astrophysics Data System (ADS)

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

    1981-07-01

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

  18. Cavity Enhanced absorption spectroscopy with an Optical Comb: Detection of atmospheric radicals in the near UV.

    NASA Astrophysics Data System (ADS)

    Méjean, G.; Kassi, S.; Romanini, D.

    2009-04-01

    The atmospheric chemistry community suffers a lack of fast, reliable and space resolved measurement for a wide set of very reactive molecules (e.g. radicals such as OH, NO3, BrO, IO, etc.). Due to their high reactivity, these molecules largely control the lifetime and concentration of numerous key atmospheric species. The concentrations of radicals are extremely low (ppbv or less) and highly variable in time and space. Measuring their concentration is often extremely laborious, expensive and requires heavy equipment (chemical sampling and treatment followed by mass spectrometry and/or chromatography). We recently introduced an optical spectroscopy technique based on a femtosecond laser oscillator, "Mode-Locked Cavity-Enhanced Absorption Spectroscopy", that we propose to develop into an instrument for in situ measurement of local concentration of traces of reactive molecules [1-3]. We have already demonstrated the possibility of measuring part in 1E12 by volume concentrations of radicals of high atmospheric interest, such as IO or BrO [4], as needed for monitoring these species in the environment. We apply cavity-enhanced absorption spectroscopy in the near UV range using a frequency-doubled Ti:Sa modelocked femtosecond laser. Efficient broadband injection of a high finesse cavity is obtained by matching this optical frequency-comb source to the comb of cavity transmission resonances. A grating spectrograph and a detector array disperse and detect the spectrum transmitted by the cavity carrying the absorption features of intracavity molecules. IO traces were obtained by mixing together controlled flows of gaseous iodine and ozone inside a high finesse cavity (F~6000). A Chameleon Ultra II ML-Laser (gracefully lent during 1 month by Coherent Inc.) was frequency doubled to address an absorption band of IO at 436 nm. A locking scheme allowed the cavity transmission to be smooth and stable. The transmitted light was dispersed using a high resolution (0.07nm) grating

  19. Observation of kinetic networks of hydrogen-bond exchange using 2D IR echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Yung Sam; Hochstrasser, Robin M.

    The ultrafast H-bond motion in acetonitrile/methanol and of methanol and water around a dicarbonyl (piperidone) dominates the mechanism of vibrational coherence transfer in linear and 2D IR echo spectra. Multiple state coherence transfer and energy transfer are seen at and between the two carbonyl groups of the piperidone in both water and methanol.

  20. Organic Spectroscopy Laboratory: Utilizing IR and NMR in the Identification of an Unknown Substance

    ERIC Educational Resources Information Center

    Glagovich, Neil M.; Shine, Timothy D.

    2005-01-01

    A laboratory experiment that emphasizes the interpretation of both infrared (IR) and nuclear magnetic resonance (NMR) spectra in the elucidation of the structure of an unknown compound was developed. The method helps students determine [to the first power]H- and [to the thirteenth power]C-NMR spectra from the structures of compounds and to…