WorldWideScience

Sample records for absorption spectroscopy studies

  1. Bioacoustic Absorption Spectroscopy

    2016-06-07

    frequencies (Ching and Weston, 1971). RESULTS Measured resonance frequencies of absorption lines, which were attributed to adult (~ 1.3 khz) and juvenile ...of adult and juvenile sardines. These results suggest that bioacoustic absorption spectroscopy measurements permit isolation of juvenile from adult...from broadband tomographic transmission loss measurements over large areas . 2. Depths of sardines and contours of phytoplankton concentrations vs. time

  2. X-ray Absorption Spectroscopy

    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.

  3. Studies of Arctic Middle Atmosphere Chemistry using Infrared Absorption Spectroscopy

    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

  4. [Near infrared Cavity enhanced absorption spectroscopy study of NO2O].

    Wu, Zhi-wei; Dong, Yan-ting; Zhou, Wei-dong

    2014-08-01

    Using a tunable near infrared external cavity diode laser and a 650 mm long high finesse optical cavity consisting of two highly reflective (R=99.97% at 6561.39 cm(-1)) plan-concave mirrors of curvature radius approximately 1000 mm, a cavity enhanced absorption spectroscopy (CEAS) system was made. The absorption spectra centered at 6561.39 cm(-1) of pure N2O gas and gas mixtures of N2O and N2 were recorded. According to the absorption of N2O at 6561.39 cm(-1) in the cavity, the measured effective absorption path was about 1460 km. The spectra line intensity and line-width of N2O centered at 6561.39 cm(-1) were carefully studied. The relationship between the line-width of absorption spectra and the gas pressure was derived. The pressure broadening parameter of N2 gas for NO2O line centered at 6 561. 39 cm(-1) was deduced and given a value of approximately (0.114 +/- 0.004) cm(-1) x atm(-1). The possibility to detect trace N2O gas in mixture using this CEAS system was investigated. By recording the ab- sorption spectra of N2O gas mixtures at different concentration, the relationship between the line intensity and gas concentration was derived. The minimum detectable absorption was found to be 2.34 x 10(-7) cm(-1) using this cavity enhanced absorption spectroscopy system. And te measurement precision in terms of relative standard deviation (RSD) for N2O is approximately 1.73%, indicating the possibility of using the cavity enhanced absorption spectroscopy system for micro gas N2O analysis in the future.

  5. Study of bulk and interface defects in silicon oxide with X-ray absorption spectroscopy

    Tallarida, Massimo [Brandenburgische Technische Universitaet, Konrad Wachsmann Allee 17, 03046 Cottbus (Germany)], E-mail: tallamas@tu-cottbus.de; Schmeisser, Dieter [Brandenburgische Technische Universitaet, Konrad Wachsmann Allee 17, 03046 Cottbus (Germany)

    2007-11-25

    We show in this work a detailed study of the SiO{sub 2}/Si interface by means of X-ray absorption spectroscopy (XAS). The Si2p absorption edge was measured for both a thick (50 nm) oxide layer and a native (1.5 nm) oxide. From the comparison between these two spectra we can address XAS features to bulk defects in SiO{sub 2} and to interface defects in the native oxide. We demonstrate the capability of XAS of achieving information about interface defects and suggest its use in more complex systems.

  6. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    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.

  7. Sensitive and rapid laser diagnostic for shock tube kinetics studies using cavity-enhanced absorption spectroscopy.

    Sun, Kai; Wang, Shengkai; Sur, Ritobrata; Chao, Xing; Jeffries, Jay B; Hanson, Ronald K

    2014-04-21

    We report the first application of cavity-enhanced absorption spectroscopy (CEAS) using a coherent light source for sensitive and rapid gaseous species time-history measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 83 with a measurement time resolution of 20 µs was demonstrated for C2H2 detection using a near-infrared transition near 1537 nm, corresponding to a noise-equivalent detection limit of 20 ppm at 296 K and 76 ppm at 906 K at 50 kHz. This substantial gain in signal, relative to conventional single-pass absorption, will enable ultra-sensitive species detection in shock tube kinetics studies, particularly useful for measurements of minor species and for studies of dilute reactive systems.

  8. The potential of UV-VIS-NIR absorption spectroscopy in glass studies

    Meulebroeck, Wendy; Baert, Kitty; Ceglia, Andrea; Cosyns, Peter; Wouters, Hilde; Nys, Karin; Terryn, Herman; Thienpont, Hugo

    Absorption spectroscopy is the technique that measures the absorption of radiation as a function of wavelength, due to its interaction with the material. During a research project funded by our home university, we were able to investigate the possibilities of this technique to study ancient glasses. One of our main conclusions is that UV-VIS-NIR absorption spectroscopy is especially suited to characterize colored artifacts in terms of composition and furnace conditions. Moreover, for naturally colored window glasses, we have shown that this technique allows us to classify fragments based on differences in iron impurity levels. It is a semi-quantitative analysis tool that can be applied for a first-line analysis of (large) glass collections. Thanks to the commercial available portable instruments, these measurements can be performed at relative high speed and this in-situ if necessary. To illustrate the possibilities of this technique, we describe in this paper two case-studies. In a first test-case we analyze 63 naturally colored window glasses and demonstrate how groups with different iron concentrations can be identified by calculating the absorption edge position from the measured optical spectrum. In a second case-study 8 modern naturally colored and 31 intentionally colored Roman glass fragments are the point of focus. For these samples we first estimate which samples are potentially fabricated under the same furnace conditions. This is done based on the calculated color values. Finally we identify the type of applied colorants.

  9. Metal release in metallothioneins induced by nitric oxide: X-ray absorption spectroscopy study.

    Casero, Elena; Martín-Gago, José A; Pariente, Félix; Lorenzo, Encarnación

    2004-12-01

    Metallothioneins (MTs) are low molecular weight proteins that include metal ions in thiolate clusters. The capability of metallothioneins to bind different metals has suggested their use as biosensors for different elements. We study here the interaction of nitric oxide with rat liver MTs by using in situ X-ray absorption spectroscopy techniques. We univocally show that the presence of NO induces the release of Zn atoms from the MT structure to the solution. Zn ions transform in the presence of NO from a tetrahedral four-fold coordinated environment in the MT into a regular octahedral six-fold coordinated state, with interatomic distances compatible with those of Zn solvated in water.

  10. Total absorption spectroscopy study of $^{92}$Rb decay: a major contributor to reactor antineutrino flux

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

    2015-01-01

    The antineutrino spectra measured in recent experiments at reactors are inconsistent with calculations based on the conversion of integral beta spectra recorded at the ILL reactor. $^{92}$Rb makes the dominant contribution to the reactor spectrum in the 5-8 MeV range but its decay properties are in question. We have studied $^{92}$Rb decay with total absorption spectroscopy. Previously unobserved beta feeding was seen in the 4.5-5.5 region and the GS to GS feeding was found to be 87.5(25)%. The impact on the reactor antineutrino spectra calculated with the summation method is shown and discussed.

  11. Total Absorption Spectroscopy Study of 92Rb Decay: A Major Contributor to Reactor Antineutrino Spectrum Shape

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

    2015-09-01

    The antineutrino spectra measured in recent experiments at reactors are inconsistent with calculations based on the conversion of integral beta spectra recorded at the ILL reactor. 92Rb makes the dominant contribution to the reactor antineutrino spectrum in the 5-8 MeV range but its decay properties are in question. We have studied 92Rb decay with total absorption spectroscopy. Previously unobserved beta feeding was seen in the 4.5-5.5 region and the GS to GS feeding was found to be 87.5(25)%. The impact on the reactor antineutrino spectra calculated with the summation method is shown and discussed.

  12. Adsorption of mercury on lignin: combined surface complexation modeling and X-ray absorption spectroscopy studies.

    Lv, Jitao; Luo, Lei; Zhang, Jing; Christie, Peter; Zhang, Shuzhen

    2012-03-01

    Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

  13. X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

    Andrews, J.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Structural Biology Div.

    1995-08-01

    In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal II EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.

  14. Electronic topological transition in zinc under pressure: An x-ray absorption spectroscopy study

    Aquilanti, G.; Trapananti, A.; Minicucci, M.; Liscio, F.; Twaróg, A.; Principi, E.; Pascarelli, S.

    2007-10-01

    Zinc metal has been studied at high pressure using x-ray absorption spectroscopy. In order to investigate the role of the different degrees of hydrostaticity on the occurrence of structural anomalies following the electronic topological transition, two pressure transmitting media have been used. Results show that the electronic topological transition, if it exists, does not induce an anomaly in the local environment of compressed Zn as a function of hydrostatic pressure and any anomaly must be related to a loss of hydrostaticity of the pressure transmitting medium. The near-edge structures of the spectra, sensitive to variations in the electronic density of states above the Fermi level, do not show any evidence of electronic transition whatever pressure transmitting medium is used.

  15. Study on synchronous detection method of methane and ethane with laser absorption spectroscopy technology

    He, Ying; Zhang, Yu-jun; You, Kun; Gao, Yan-wei; Chen, Chen; Liu, Jian-guo; Liu, Wen-qing

    2016-10-01

    The main ingredient of mash gas is alkenes, and methane is the most parts of mash gas and ethane is a small portion of it. Fast, accurate, real-time measurement of methane and ethane concentration is an important task for preventing coal mining disaster. In this research, a monitoring system with tunable diode laser absorption spectroscopy (TDLAS) technology has been set up for simultaneous measurement of methane and ethane, and a DFB laser at wavelength of 1.653μm was used as the laser source. The absorption spectroscopy information of methane and ethane, especially the characteristic of the spectrum peak positions and relative intensity were determined by available spectral structures from previous study and available database. Then, the concentration inversion algorithm method based on the spectral resolution and feature extraction was designed for methane and ethane synchronous detection. At last, the continuously experimental results obtained by different concentration of methane and ethane sample gases with the multiple reflection cell and the standard distribution system. In this experiment, the standard distribution system made with the standard gas and two high precision mass flow meters of D07 Sevenstar series whose flow velocity is 1l/min and 5l/min respectively. When the multiple reflection cell work stably, the biggest detection error of methane concentration inversion was 3.7%, and the biggest detection error of ethane was 4.8%. So it is verified that this concentration inversion algorithm works stably and reliably. Thus, this technology could realize the real-time, fast and continuous measurement requirement of mash gas and it will provide the effective technical support to coal mining production in safety for our country.

  16. [Dithiobis-succinimidyl propionate on gold island films: surface-enhanced infrared absorption spectroscopy study].

    Guo, Hao; Ding, Li; Zhang, Tian-Jie; Mao, Yan-Li

    2013-05-01

    Dithiobis-succinimidyl propionate (DTSP), an important homobifunctional crosslinker, has been widely used for the covalent immobilization of proteins onto solid supports by amine coupling. In the present study, adsorption of DTSP on vacuum-deposited gold island films was analyzed by means of surface-enhanced infrared absorption spectroscopy (SEIRAS). For the sake of a reliable assignment of the vibrational spectra, IR intensity of the adsorption model of TSP on one gold surface was calculated using density functional theory (DFT) at the Beck' s three-parameter Lee-Yang-Parr (B3LYP) level with the LANL2DZ basis set. SEIRAS and multiple-angle-of-incidence polarization infrared reflection-absorption spectroscopy indicated that TSP is arranged orderly in a tilted fashion with a dihedral angle of 65 degrees between the plane of succinimidyl ring and the gold surface. The binding kinetics revealed that that the time constant of self-assembly of the TSP layer is 220 sec. Furthermore, the coupling process of amino-nitrilotriacetic acid (ANTA) with surface-bound TSP monolayer was monitored in situ by SEIRAS. Three negative bands observed at 1 807, 1 776, and 1 728 cm(-1) respectively provided direct evidence for the reaction of the succinimidyl ester. The appearance of one intense band at 1 566 cm(-1) gave a clear support for the presence of the cross-link between ANTA and TSP. We hope that the results in current investigation will contribute to the better understanding of properties of DTSP and related reactions at the molecular level.

  17. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

  18. Theory of attosecond absorption spectroscopy in krypton

    Baggesen, Jan Conrad; Lindroth, Eva; Madsen, Lars Bojer

    2012-01-01

    A theory for time-domain attosecond pump–attosecond probe photoabsorption spectroscopy is formulated and related to the atomic response. The theory is illustrated through a study of attosecond absorption spectroscopy in krypton. The atomic parameters entering the formulation such as energies...... of the hole in this manner. In a second example, a hole is created in an inner shell by the first pulse, and the second probe pulse couples an even more tightly bound state to that hole. The hole decays in this example by Auger electron emission, and the absorption spectroscopy follows the decay of the hole...

  19. Synchrotron soft X-ray absorption spectroscopy study of carbon and silicon nanostructures for energy applications.

    Zhong, Jun; Zhang, Hui; Sun, Xuhui; Lee, Shuit-Tong

    2014-12-10

    Carbon and silicon materials are two of the most important materials involved in the history of the science and technology development. In the last two decades, C and Si nanoscale materials, e.g., carbon nanotubes, graphene, and silicon nanowires, and quantum dots, have also emerged as the most interesting nanomaterials in nanoscience and nanotechnology for their myriad promising applications such as for electronics, sensors, biotechnology, etc. In particular, carbon and silicon nanostructures are being utilized in energy-related applications such as catalysis, batteries, solar cells, etc., with significant advances. Understanding of the nature of surface and electronic structures of nanostructures plays a key role in the development and improvement of energy conversion and storage nanosystems. Synchrotron soft X-ray absorption spectroscopy (XAS) and related techniques, such as X-ray emission spectroscopy (XES) and scanning transmission X-ray microscopy (STXM), show unique capability in revealing the surface and electronic structures of C and Si nanomaterials. In this review, XAS is demonstrated as a powerful technique for probing chemical bonding, the electronic structure, and the surface chemistry of carbon and silicon nanomaterials, which can greatly enhance the fundamental understanding and also applicability of these nanomaterials in energy applications. The focus is on the unique advantages of XAS as a complementary tool to conventional microscopy and spectroscopy for effectively providing chemical and structural information about carbon and silicon nanostructures. The employment of XAS for in situ, real-time study of property evolution of C and Si nanostructures to elucidate the mechanisms in energy conversion or storage processes is also discussed.

  20. Bioavailability study of calcium sandoz-250 by atomic absorption spectroscopy in albino rats

    Patel, Bimalkumar N.; Krishnaveni, N.; Jivani, Nurrrudin P.; Khodakiya, Akruti S.; Khodakiya, Moorti S.; Parida, Saswat K.

    2014-01-01

    Background: Calcium sandoz-250 is an Ayurvedic calcium supplement, containing Khatika Churna. Bioavailability study of the formulation is essential for estimation of peak plasma concentration (C max), time to C max and rate of absorption. Aim: To evaluate the absorption parameters of calcium sandoz-250 in albino rats by atomic absorption spectroscopic (AAS) method. Materials and Methods: Study was carried out as a single dose, open-label, randomized study. Estimation of calcium was carried ou...

  1. Non-invasive gas monitoring in newborn infants using diode laser absorption spectroscopy: a case study

    Lundin, Patrik; Svanberg, Emilie K.; Cocola, Lorenzo; Lewander, Märta; Andersson-Engels, Stefan; Jahr, John; Fellman, Vineta; Svanberg, Katarina; Svanberg, Sune

    2012-03-01

    Non-invasive diode laser spectroscopy was, for the first time, used to assess gas content in the intestines and the lungs of a new-born, 4 kg, baby. Two gases, water vapor and oxygen, were studied with two low-power tunable diode lasers, illuminating the surface skin tissue and detecting the diffusely emerging light a few centimeters away. The light, having penetrated into the tissue, had experienced absorption by gas located in the lungs and in the intestines. Very distinct water vapor signals were obtained from the intestines while imprint from oxygen was lacking, as expected. Detectable, but minor, signals of water vapor were also obtained from the lungs, illuminating the armpit area and detecting below the collar bone. Water vapor signals were seen but again oxygen signals were lacking, now due to the difficulties of penetration of the oxygen probing light into the lungs of this full-term baby. Ultra-sound images were obtained both from the lungs and from the stomach of the baby. Based on dimensions and our experimental findings, we conclude, that for early pre-term babies, also oxygen should be detectable in the lungs, in addition to intestine and lung detection of water vapor. The present paper focuses on the studies of the intestines while the lung studies will be covered in a forthcoming paper.

  2. Studies of ionic liquid solutions by soft X-ray absorption spectroscopy

    Rodrigues, Fabio [Departamento de Quimica Fundamental, Instituto de Quimica, Universidade de Sao Paulo, CP 26.077, CEP 05513-970, Sao Paulo, SP (Brazil); Nascimento, Gustavo M. do [Departamento de Quimica Fundamental, Instituto de Quimica, Universidade de Sao Paulo, CP 26.077, CEP 05513-970, Sao Paulo, SP (Brazil)], E-mail: morari@yahoo.com; Santos, Paulo S. [Departamento de Quimica Fundamental, Instituto de Quimica, Universidade de Sao Paulo, CP 26.077, CEP 05513-970, Sao Paulo, SP (Brazil)

    2007-03-15

    Soft X-ray spectroscopies give specific information about the electronic structure around light elements. The high absorption of soft X-rays by almost every molecule, including air, requires studies under vacuum, which represents a great limitation. Solids with high vapor pressure and liquids are very difficult to be studied, making solution chemistry almost neglected. This work explores the use of ionic liquids, organic liquids with very low vapor pressure, as media to study chemical solutions using soft X-ray. N 1s spectra are reported of ionic liquid solutions of 1-methyl-3alkyl-imidazolium cation with different anions and chain lengths, and urea/choline chloride mixtures (a deep eutectic solvent) with several solutes including dyes (Janus Green B and Congo Red), synthetic polymers (polyaniline) and nitrate salts. While there are significant problems with the signal of the solvent, the results do show that it is possible to detect solute signals, and further to see spectral changes attributed to solvent-solute interactions.

  3. Application of X-ray Absorption Spectroscopy to the study of nuclear structural materials

    Liu, Shanshan

    One of key technologies for the next generation nuclear systems are advanced materials, including high temperature structural materials, fast neutron resistance core materials and so on. Local structure determination in these systems, which often are crystallographically intractable, is critical to gaining an understanding of their properties. In this thesis, X-ray Absorption Spectroscopy (XAS), including Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES), is used to examine the geometric and electronic structure of nuclear structural materials under varying conditions. The thesis is divided into two main sections. The first examines the structural analysis of nanostructured ferritic alloys (NFA) which are dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features, resulting in remarkable high temperature creep strength and radiation damage resistance. Titanium and Yttrium K-edge XAS shows commercial alloys MA957 and J12YWT more closely resemble the as received Fe-14Cr-3W-0.4Ti (wt. %) powders, and mechanically alloyed (MA) powders with 0.25Y2O3 (wt. %). It shows that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix. In contrast, annealed powders and hot isostatic press (HIP) consolidated alloys show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. The second section describes corrosion studies of Pb with 316L stainless steel, molybdenum and spinet (MgAl2O4) at high temperature by XAS. The corrosion of fuel cladding and structural materials by liquid lead at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. The results of ex-situ studies show that a Mo substrate retained a smooth and less corroded surface than 316L stainless steel sample at elevated temperature. In

  4. Microbeam x-ray absorption spectroscopy study of chromium in large-grain uranium dioxide fuel

    Mieszczynski, C.; Kuri, G.; Bertsch, J.; Martin, M.; Borca, C. N.; Delafoy, Ch; Simoni, E.

    2014-09-01

    Synchrotron-based microprobe x-ray absorption spectroscopy (XAS) has been used to study the local atomic structure of chromium in chromia-doped uranium dioxide (UO2) grains. The specimens investigated were a commercial grade chromia-doped UO2 fresh fuel pellet, and materials from a spent fuel pellet of the same batch, irradiated with an average burnup of ~40 MW d kg-1. Uranium L3-edge and chromium K-edge XAS have been measured, and the structural environments of central uranium and chromium atoms have been elucidated. The Fourier transform of uranium L3-edge extended x-ray absorption fine structure shows two well-defined peaks of U-O and U-U bonds at average distances of 2.36 and 3.83 Å. Their coordination numbers are determined as 8 and 11, respectively. The chromium Fourier transform extended x-ray absorption fine structure of the pristine UO2 matrix shows similar structural features with the corresponding spectrum of the irradiated spent fuel, indicative of analogous chromium environments in the two samples studied. From the chromium XAS experimental data, detectable next neighbor atoms are oxygen and uranium of the cation-substituted UO2 lattice, and two distinct subshells of chromium and oxygen neighbors, possibly because of undissolved chromia particles present in the doped fuels. Curve-fitting analyses using theoretical amplitude and phase-shift functions of the closest Cr-O shell and calculations with ab initio computer code FEFF and atomic clusters generated from the chromium-dissolved UO2 structure have been carried out. There is a prominent reduction in the length of the adjacent Cr-O bond of about 0.3 Å in chromia-doped UO2 compared with the ideal U-O bond length in standard UO2 that would be expected because of the change in effective Coulomb interactions resulting from replacing U4+ with Cr3+ and their ionic size differences. The contraction of shortest Cr-U bond is ~0.1 Å relative to the U-U bond length in bulk UO2. The difference in the

  5. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    Collingwood, J.F.; Mikhaylova, A.; Davidson, M.R.; Batich, C.; Streit, W.J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R.S.; Dobson, J. (IIT); (Keele); (Florida); (DRDC)

    2008-06-16

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (< 5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterize anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution {approx} 5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  6. X-ray absorption spectroscopy study on the thermal and hydrazine reduction of graphene oxide

    Liang, Xianqing, E-mail: lxq@gxu.edu.cn [The Colleague of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Wang, Yu [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China); Zheng, Huiyuan [The Colleague of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Wu, Ziyu, E-mail: wuzy@ustc.edu.cn [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)

    2014-10-15

    Highlights: • XAS study of GO and reduced GO was performed. • Detailed evolution of the electronic structures and chemical bonding of GO was revealed. • A new efficient route for the reduction of GO is proposed. - Abstract: X-ray absorption spectroscopy (XAS) was applied to systemically investigate the deoxygenation of graphene oxide (GO) via annealing and hydrazine treatment. Detailed evolution of the electronic structures and chemical bonding of GO was presented. The enhanced intensity of π{sup *} resonance and the appearance of splitting σ{sup *} resonance in C K-edge XAS spectra suggest high extents of recoveries of π-conjugation upon reduction using thermal annealing or hydrazine. Experimental results revealed that the carboxyl as well as epoxide and hydroxyl groups on the surface of GO were thermally reduced first, followed by the more difficult removal of carbonyl and cyclic ether groups at higher temperatures. The hydrazine reduction could remove epoxide, hydroxyl and carboxyl groups effectively, whereas the carbonyl groups were partially reduced with the incorporation of nitrogen species simultaneously. The residual oxygen functional groups on hydrazine-reduced GO could be further removed after modest thermal annealing. It was proposed that a combination of both types of reductions would give the best deoxygenation efficiency for the production of graphene.

  7. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  8. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  9. Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

    2015-07-01

    AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A

  10. Strontium Localization in Bone Tissue Studied by X-Ray Absorption Spectroscopy

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Ståhl, Kenny

    2014-01-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X...... structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas...

  11. A new cell for X-ray absorption spectroscopy study under high pressure

    ZHENG Li-Rong; CHE Rong-Zheng; LIU Jing; DU Yong-Hua; ZHOU Ying-Li; HU Tian-Dou

    2009-01-01

    X-ray absorption fine structure (XAFS) spectroscopy is a powerful technique for the investigation of the local environment around selected atoms in condensed matter. XAFS under pressure is an important method for the synchrotron source. We design a cell for a high pressure XAFS experiment. Sintered boron carbide is used as the anvils of this high pressure cell in order to obtain a full XAFS spectrum free from diffraction peaks. In addition, a hydraulic pump was adopted to make in-suit pressure modulation. High quality XAFS spectra of ZrH2 under high pressure (up to 13 Gpa) were obtained by this cell.

  12. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  13. Feasibility study of mid-infrared absorption spectroscopy using electrospray ionization

    Ahmed, Tahsin; Foster, Erick; Bohn, Paul; Howard, Scott

    2016-09-01

    Precise detection of trace amount of molecules, such as the disease biomarkers present in biofluids or explosive residues, requires high sensitivity detection. electrospray ionization-mass spectrometry (ESI-MS) is a common and effective technique for sensitive trace molecular detection in small-volume liquid samples. In ESI-MS, nano-liter volume samples are ionized and aerosolized by ESI, and fed into MS for mass analysis. ESI-MS has proven to be a reliable ionization technique for coupling liquid phase separations like liquid chromatography (LC) and capillary zone electrophoresis (CE) with the highly specific resolving power of MS. While CE and ESI can be performed on a microfluidic chip having a footprint of a few cm2, MS is typically at least 100 times bigger in size than a micro-chip. A reduced size, weight, and power profile would enable semi-portable applications in forensics, environmental monitoring, defense, and biological/pharmaceutical applications. To achieve this goal, we present an initial study evaluating the use of mid-infrared absorption spectroscopy (MIRAS) in place of MS to create a ESI-MIRAS system. To establish feasibility, we perform ESI-MIRAS on phospholipid samples, which have been previously demonstrated to be separable by CE. Phospholipids are biomarkers of degenerative neurological, kidney, and bone diseases and can be found in biofluids such as blood, urine and cerebrospinal fluid. To establish sensitivity limits, calibration samples of 100 μM concentration are electrospray deposited on to a grounded Si wafer for different times (1 minutes to 4 minutes with a 1 minute step). The minimum detectable concentration-time product, where a FTIR globar is used as the MIR source, is found 200 μM·s.

  14. Chemometric analysis of femtosecond transient absorption spectroscopy data:Study of the photochromism of anils

    Cyril; RUCKEBUSCH; Nicolas; MOUTON; Thomas; GLADYTZ; Anika; RENDELMANN; Guy; BUNTINX; Michel; SLIWA

    2010-01-01

    Chemometric methods are applied for the purpose of extracting relevant information from transient absorption spectroscopy data probing the photochromism of molecules from the family of salicylidene aniline. The process consists of an ultrafast excited state intramolecular proton transfer occurring from an enol form which is then followed by a cis-trans isomerization to finally reach a trans-keto photo-product. This work focuses on the potential of combining multivariate curve resolution for modeling pure profiles and two dimensional correlation spectroscopy data analysis for providing information on the dynamics of spectral features. The results obtained for one derivative of salicylidene aniline provide information regarding the number of species created after the proton transfer and characterization of their absorption spectra and their kinetics in the picosecond time scale. The spectral resolution of two cis-keto* forms is proposed for the first time. It is also found that both cis-keto* species are involved in the formation of the trans-keto photo-product. The main precursor of the trans-keto photo-product is the cis-keto* form which has the shortest characteristic time.

  15. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

    Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

    2017-01-01

    Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements. PMID:28186190

  16. Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

    Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

    2017-02-01

    Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

  17. Voltage-controlled magnetic anisotropy in Fe|MgO tunnel junctions studied by x-ray absorption spectroscopy

    Miwa, Shinji, E-mail: miwa@mp.es.osaka-u.ac.jp; Matsuda, Kensho; Tanaka, Kazuhito; Goto, Minori; Suzuki, Yoshishige [Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Kotani, Yoshinori; Nakamura, Tetsuya [Japan Synchrotron Radiation Research Institute/SPring-8, Sayo, Hyogo 679-5198 (Japan)

    2015-10-19

    In this study, voltage-controlled magnetic anisotropy (VCMA) in Fe|MgO tunnel junctions was investigated via the magneto-optical Kerr effect, soft x-ray absorption spectroscopy, and magnetic circular dichroism spectroscopy. The Fe|MgO tunnel junctions showed enhanced perpendicular magnetic anisotropy under external negative voltage, which induced charge depletion at the Fe|MgO interface. Despite the application of voltages of opposite polarity, no trace of chemical reaction such as a redox reaction attributed to O{sup 2−} migration was detected in the x-ray absorption spectra of the Fe. The VCMA reported in the Fe|MgO-based magnetic tunnel junctions must therefore originate from phenomena associated with the purely electric effect, that is, surface electron doping and/or redistribution induced by an external electric field.

  18. X-ray absorption spectroscopy of metalloproteins.

    Ward, Jesse; Ollmann, Emily; Maxey, Evan; Finney, Lydia A

    2014-01-01

    Metalloproteins are enormously important in biology. While a variety of techniques exist for studying metals in biology, X-ray absorption spectroscopy is particularly useful in that it can determine the local electronic and physical structure around the metal center, and is one of the few avenues for studying "spectroscopically silent" metal ions like Zn(II) and Cu(I) that have completely filled valence bands. While X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are useful for studying metalloprotein structure, they suffer the limitation that the detected signal is an average of all the various metal centers in the sample, which limits its usefulness for studying metal centers in situ or in cell lysates. It would be desirable to be able to separate the various proteins in a mixture prior to performing X-ray absorption studies, so that the derived signal is from one species only. Here we describe a method for performing X-ray absorption spectroscopy on protein bands following electrophoretic separation and western blotting.

  19. X-ray absorption spectroscopy studies of electrochemically deposited thin oxide films.

    Balasubramanian, M.

    1998-06-02

    We have utilized ''in situ'' X-ray Absorption Fine Structure Spectroscopy to investigate the structure and composition of thin oxide films of nickel and iron that have been prepared by electrodeposition on a graphite substrate from aqueous solutions. The films are generally disordered. Structural information has been obtained from the analysis of the data. We also present initial findings on the local structure of heavy metal ions, e.g. Sr and Ce, incorporated into the electrodeposited nickel oxide films. Our results are of importance in a number of technological applications, among them, batteries, fuel cells, electrochromic and ferroelectric materials, corrosion protection, as well as environmental speciation and remediation.

  20. Atomic absorption spectroscopy in ion channel screening.

    Stankovich, Larisa; Wicks, David; Despotovski, Sasko; Liang, Dong

    2004-10-01

    This article examines the utility of atomic absorption spectroscopy, in conjunction with cold flux assays, to ion channel screening. The multiplicity of ion channels that can be interrogated using cold flux assays and atomic absorption spectroscopy is summarized. The importance of atomic absorption spectroscopy as a screening tool is further elaborated upon by providing examples of the relevance of ion channels to various physiological processes and targeted diseases.

  1. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level.

  2. Electronic structure of fluorinated multiwalled carbon nanotubes studied using x-ray absorption and photoelectron spectroscopy

    Brzhezinskaya, M. M.; Muradyan, V. E.; Vinogradov, N. A.; Preobrajenski, A. B.; Gudat, W.; Vinogradov, A. S.

    2009-04-01

    This paper presents the results of combined investigation of the chemical bond formation in fluorinated multiwalled carbon nanotubes (MWCNTs) with different fluorine contents (10-55wt%) and reference compounds (highly oriented pyrolytic graphite crystals and “white” graphite fluoride) using x-ray absorption and photoelectron spectroscopy at C1s and F1s thresholds. Measurements were performed at BESSY II (Berlin, Germany) and MAX-laboratory (Lund, Sweden). The analysis of the soft x-ray absorption and photoelectron spectra points to the formation of covalent chemical bonding between fluorine and carbon atoms in the fluorinated nanotubes. It was established that within the probing depth (˜15nm) of carbon nanotubes, the process of fluorination runs uniformly and does not depend on the fluorine concentration. In this case, fluorine atoms interact with MWCNTs through the covalent attachment of fluorine atoms to graphene layers of the graphite skeleton (phase 1) and this bonding is accompanied by a change in the hybridization of the 2s and 2p valence electron states of the carbon atom from the trigonal (sp2) to tetrahedral (sp3) hybridization and by a large electron transfer between carbon an fluorine atoms. In the MWCNT near-surface region the second fluorine-carbon phase with weak electron transfer is formed; it is located mainly within two or three upper graphene monolayers, and its contribution becomes much poorer as the probing depth of fluorinated multiwalled carbon nanotubes (F-MWCNTs) increases. The defluorination process of F-MWCNTs on thermal annealing has been investigated. The conclusion has been made that F-MWCNT defluorination without destruction of graphene layers is possible.

  3. Spectral studies of ocean water with space-borne sensor SCIAMACHY using Differential Optical Absorption Spectroscopy (DOAS

    M. Vountas

    2007-09-01

    Full Text Available Methods enabling the retrieval of oceanic parameter from the space borne instrumentation Scanning Imaging Absorption Spectrometer for Atmospheric ChartographY (SCIAMACHY using Differential Optical Absorption Spectroscopy (DOAS are presented. SCIAMACHY onboard ENVISAT measures back scattered solar radiation at a spectral resolution (0.2 to 1.5 nm. The DOAS method was used for the first time to fit modelled Vibrational Raman Scattering (VRS in liquid water and in situ measured phytoplankton absorption reference spectra to optical depths measured by SCIAMACHY. Spectral structures of VRS and phytoplankton absorption were clearly found in these optical depths. Both fitting approaches lead to consistent results. DOAS fits correlate with estimates of chlorophyll concentrations: low fit factors for VRS retrievals correspond to large chlorophyll concentrations and vice versa; large fit factors for phytoplankton absorption correspond with high chlorophyll concentrations and vice versa. From these results a simple retrieval technique taking advantage of both measurements is shown. First maps of global chlorophyll concentrations were compared to the corresponding MODIS measurements with very promising results. In addition, results from this study will be used to improve atmospheric trace gas DOAS-retrievals from visible wavelengths by including these oceanographic signatures.

  4. [Study on experiment of absorption spectroscopy detection of pesticide residues of carbendazim in orange juice].

    Ji, Ren-Dong; Chen, Meng-Lan; Zhao, Zhi-Min; Zhu, Xing-Yue; Wang, Le-Xin; Liu, Quan-Jin

    2014-03-01

    Absorption spectra were studied for the carbendazim, in the mixed solution of orange juice and carbendazim using spectrophotometer. The most intensive characteristic peak (285 nm) was found in the spectrum of carbendazim standard solution. Compared with the carbendazim drug solution, the peak position of absorption spectrum has the blue shift (285-280 nm) when carbendazim (0.28 mg x mL(-1))was added in the orange juice. So that we can conclude that interaction happened between the orange juice and carbendazim. Through the method of least squares fitting, the prediction models between the absorbance of orange juice and carbendazim content was obtained with a good linear relationship. The linear function model was: I = 2.41 + 9.26x, the correlation coefficient was 0.996, and the recovery was: 81%-102%. According to the regression model, we can obtain the amount of carbendazim pesticide residues in orange juice. It was verified that the method of using ultraviolet-visible absorption spectra was feasible to detect the carbendazim residues in orange juice. The result proved that it is possible to detect pesticide residues of carbendazim in orange juice, and it can meet the needs of rapid analysis. This study provides a new way for the detection of pesticide residues.

  5. Pump-flow-probe x-ray absorption spectroscopy as a tool for studying aintermediate states of photocatalytic systems

    Smolentsev, Grigory; Guda, Alexander; Zhang, Xiaoyi

    2013-01-01

    A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time resolution of tens of microseconds and high detection efficiency for samples with sub-millimolar concentr......A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time resolution of tens of microseconds and high detection efficiency for samples with sub...

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

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

    2015-01-01

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

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

    Lee, Geon Joon, E-mail: gjlee@kw.ac.kr; Sim, Geon Bo; Choi, Eun Ha [Plasma Bioscience Research Center/Department of Electrical and Biological Physics, Kwangwoon University, Seoul 139-701 (Korea, Republic of); Kwon, Young-Wan [KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul 136-701 (Korea, Republic of); Kim, Jun Young; Jang, Siun; Kim, Seong Hwan, E-mail: piceae@naver.com [Department of Microbiology and Institute of Basic Sciences, Dankook University, Cheonan 330-714 (Korea, Republic of)

    2015-01-14

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

  8. A reaction cell with sample laser heating for in situ soft X-ray absorption spectroscopy studies under environmental conditions.

    Escudero, Carlos; Jiang, Peng; Pach, Elzbieta; Borondics, Ferenc; West, Mark W; Tuxen, Anders; Chintapalli, Mahati; Carenco, Sophie; Guo, Jinghua; Salmeron, Miquel

    2013-05-01

    A miniature (1 ml volume) reaction cell with transparent X-ray windows and laser heating of the sample has been designed to conduct X-ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H2 Fischer-Tropsch reactions on Co nanoparticles.

  9. Conformational aspects of proteins at the air/water interface studied by infrared reflection-absorption spectroscopy

    Martin, A.H.; Meinders, M.B.J.; Bos, M.A.; Cohen Stuart, M.A.; Vliet, T. van

    2003-01-01

    From absorption spectra obtained with infrared reflection - absorption spectroscopy (IRRAS), it is possible to obtain information on conformational changes at a secondary folding level of proteins adsorbed at the air/water interface. In addition, information on protein concentration at the interface

  10. Carbon dioxide adsorption on a ZnO(101[combining macron]0) substrate studied by infrared reflection absorption spectroscopy.

    Buchholz, Maria; Weidler, Peter G; Bebensee, Fabian; Nefedov, Alexei; Wöll, Christof

    2014-01-28

    The adsorption of carbon dioxide on the mixed-terminated ZnO(101[combining macron]0) surface of a bulk single crystal was studied by UHV Infrared Reflection Absorption Spectroscopy (IRRAS). In contrast to metals, the classic surface selection rule for IRRAS does not apply to bulk oxide crystals, and hence vibrational bands can also be observed for s-polarized light. Although this fact substantially complicates data interpretation, a careful analysis allows for a direct determination of the adsorbate geometry. Here, we demonstrate the huge potential of IR-spectroscopy for investigations on oxide single crystal surfaces by considering all three components of the incident polarized light separately. We find that the tridentate (surface) carbonate is aligned along the [0001] direction. A comparison to data reported previously for CO2 adsorbed on the surfaces of ZnO nanoparticles provides important insight into the role of defects in the surface chemistry of powder particles.

  11. Characterization and DNA binding studies of unexplored imidazolidines by electronic absorption spectroscopy and cyclic voltammetry.

    Shah, Afzal; Nosheen, Erum; Munir, Shamsa; Badshah, Amin; Qureshi, Rumana; Rehman, Zia-Ur-; Muhammad, Niaz; Hussain, Hidayat

    2013-03-05

    UV-Vis spectroscopic behavior of four imidazolidine derivatives i.e., [5-benzylideneimidazolidine-2,4-dione (NBI), 5-(2-hydroxybenzylidene)imidazolidine-2,4-dione (HBI), 5-(4-methoxybenzylidene)imidazolidine-2,4-dione (MBI) and 5-(3,4-di-methoxybenzylidene)imidazolidine-2,4-dione (DBI)] was studied in a wide pH range. Spectroscopic response of the studied compounds was found sensitive to pH and the attached substituents. Incited by anti-tumor activity, structural miscellany and biological applications of imidazolidines, the DNA binding affinity of some novel derivatives of this class of compounds was examined by cyclic voltammetry (CV) and UV-Vis spectroscopy at pH values of blood (7.4) and lysosomes (4.5). The CV results showed the following order of binding strength: KNBI (6.40×10(6)M(-1))>KHBI (1.77×10(5)M(-1))>KMBI (2.06×10(4)M(-1))>KDBI (1.01×10(4)M(-1)) at pH 7.4. The same order was also obtained from UV-Vis spectroscopy. The greater affinity of NBI justified its preferred candidature as an effective anti-cancer drug. The DNA binding propensity of these compounds was found comparable or greater than most of the clinically used anticancer drugs.

  12. Ultra-fast X-ray absorption spectroscopy for the study of matter in transient regime; Spectroscopie d'absorption ultra-rapide de rayonnement X pour l'etude de la matiere en regime transitoire

    Lecherbourg, L

    2007-12-15

    In this work, we study the physics of dense matter, plasmas or solids, using X-ray absorption spectroscopy. Through the use of sources produced by laser-matter interaction, we have measured the absorption spectra of aluminum and bromine plasmas, as well as those of vanadium dioxide (VO{sub 2}). The measurement of absorption coefficients allows us to probe the dense matter and to study its properties. The experiments are carried out following the same principle: they use the same experimental set-up, called pump-probe. When the matter is dense, the absorption properties of an atom are modified by the surrounding environment. In a plasma, it is mainly the bound- bound transitions which are altered: the shapes of those spectral rays are modified. In a solid, the position of the neighbouring atoms in relation to the absorbing atom modify the structure of absorption levels (bound-free transition). The study of this structure allows us to measure the parameters of the material, and provides information such as the state of the electronic band or the interatomic gaps. The experiments carried out at the LULI have allowed us to probe plasmas in the relatively unknown regime of the Warm Dense Matter. One of the key parameters is that the plasma is characterised independently (FDI diagnostic). It allows for a better comparison of the measured absorption against a calculation made with the numerical model OPA-S. The experiments carried out at INRS have led to the realisation of an experimental system having the characteristics which allow the study of the dynamics of solids showing ultra-fast phase transition. For those experiments, we have used vanadium dioxide as a model system allowing us to test the feasibility of the method. (author)

  13. Study on the Interaction between CdSe Quantum Dots and Bovine Serum Albumin with Ultraviolet Visible Absorption Spectroscopy

    He You HAN; De Hong HU; Jian Gong LIANG; Zong Hai SHENG

    2006-01-01

    The interaction of CdSe quantum dots (QDs) with bovine serum albumin (BSA) has been investigated with ultraviolet visible absorption spectroscopy (UVAS). It was found that the absorption intensity of CdSe QDs significantly decreased after adding BSA solution, showing that CdSe QDs were bonded to BSA. The binding molar ratio was 1:1 and the binding constant was 9.7 × 106 L mol-1.

  14. Electronic structure of nickel porphyrin NiP: Study by X-ray photoelectron and absorption spectroscopy

    Svirskiy, G. I.; Sergeeva, N. N.; Krasnikov, S. A.; Vinogradov, N. A.; Sergeeva, Yu. N.; Cafolla, A. A.; Preobrajenski, A. B.; Vinogradov, A. S.

    2017-02-01

    Energy distributions and properties of the occupied and empty electronic states for a planar complex of nickel porphyrin NiP are studied by X-ray photoemission and absorption spectroscopy techniques. As a result of the analysis of the experimental spectra of valence photoemission, the nature and energy positions of the highest occupied electronic states were determined: the highest occupied state is formed mostly by atomic states of the porphine ligand; the following two states are associated with 3 d states of the nickel atom. It was found that the lowest empty state is specific and is described by the σ-type b 1 g MO formed by empty Ni3{d_{{x^2} - {y^2}}}-states and occupied 2 p-states of lone electron pairs of nitrogen atoms. This specific nature of the lowest empty state is a consequence of the donor-acceptor chemical bond in NiP.

  15. An X-Ray Absorption Spectroscopy Study of Ball-Milled Lithium Tantalate and Lithium Titanate Nanocrystals

    Chadwick, A. V.; Pickup, D. M.; Ramos, S.; Cibin, G.; Tapia-Ruiz, N.; Breuer, S.; Wohlmuth, D.; Wilkening, M.

    2017-02-01

    Previous work has shown that nanocrystalline samples of lithium tantalate and titanate prepared by high-energy milling show unusually high lithium ion conductivity. Here, we report an X-ray absorption spectroscopy (XAS) study at the Ti K-edge and the Ta L3 edge of samples that have been milled for various lengths of time. For both systems the results show that milling creates amorphous material whose quantity increases with the milling time. The more extensive data for the tantalate shows that milling for only 30 minutes generates ∼25% amorphous content in the sample. The content rises to ∼60% after 16 hours. It is suggested that it is the motion of the lithium ions through the amorphous content that provides the mechanism for the high ionic conductivity.

  16. Incorporation of Trace Elements in Ancient and Modern Human Bone: An X-Ray Absorption Spectroscopy Study

    Pingitore, N. E.; Cruz-Jimenez, G.; Price, T. D.

    2001-12-01

    X-ray absorption spectroscopy (XAS) affords the opportunity to probe the atomic environment of trace elements in human bone. We are using XAS to investigate the mode(s) of incorporation of Sr, Zn, Pb, and Ba in both modern and ancient (and thus possibly altered) human and animal bone. Because burial and diagenesis may add trace elements to bone, we performed XAS analysis on samples of pristine contemporary and ancient, buried human and animal bone. We assume that deposition of these elements during burial occurs by processes distinct from those in vivo, and this will be reflected in their atomic environments. Archaeologists measure strontium in human and animal bone as a guide to diet. Carnivores show lower Sr/Ca ratios than their herbivore prey due to discrimination against Sr relative to Ca up the food chain. In an initial sample suite no difference was observed between modern and buried bone. Analysis of additional buried samples, using a more sensitive detector, revealed significant differences in the distance to the second and third neighbors of the Sr in some of the buried samples. Distances to the first neighbor, oxygen, were similar in all samples. Zinc is also used in paleo-diet studies. Initial x-ray absorption spectroscopy of a limited suite of bones did not reveal any differences between modern and buried samples. This may reflect the limited number of samples examined or the low levels of Zn in typical aqueous solutions in soils. Signals from barium and lead were too low to record useful XAS spectra. Additional samples will be studied for Zn, Ba, and Pb. We conducted our XAS experiments on beam lines 4-1 and 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a Lytle detector and appropriate filter, and a solid state, 13-element Ge-detector.

  17. Excited-State Dynamics of Carotenoids Studied by Femtosecond Transient Absorption Spectroscopy

    Lee, Ingu; Pang, Yoonsoo [Department of Physics and Photon Science, Gwangju (Korea, Republic of); Lee, Sebok [Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of)

    2014-03-15

    Carotenoids, natural antenna pigments in photosynthesis share a symmetric backbone of conjugated polyenes. Contrary to the symmetric and almost planar geometries of carotenoids, excited state structure and dynamics of carotenoids are exceedingly complex. In this paper, recent infrared and visible transient absorption measurements and excitation dependent dynamics of 8'-apo-β-caroten-8'-al and 7',7'-dicyano-7'-apo-β-carotene will be reviewed. The recent visible transient absorption measurements of 8'-apo-β-caroten-8'-al in polar and nonpolar solvents will also be introduced to emphasize the complex excited-state dynamics and unsolved problems in the S{sub 2} and S{sub 1} excited states.

  18. Shock induced chemistry in liquids studied with ultrafast dynamic ellipsometry and visible transient absorption spectroscopy.

    Dang, N C; Bolme, C A; Moore, D S; McGrane, S D

    2012-10-25

    The response to ultrafast laser shock loading of nine liquids was monitored in an effort to reveal evidence of chemical changes occurring during the first 350 ps following the shock front. In an effort to compare molecular structures possessing a variety of common bonding patterns, data were acquired for the liquids: cyclohexane, cyclohexene, 1,3-cyclohexadiene, benzene, water, acetonitrile, acrylonitrile, tert-butylacetylene, and phenylacetylene. Transient absorption spectra were measured in the spectral region from 440 to 780 nm over shock stress states from 7 to 20 GPa. Ultrafast dynamic ellipsometry was used to measure the shock and particle velocity as well as the shocked refractive index. Significant transient absorption attributed to chemical reaction was observed for shocked phenylacetylene and acrylonitrile. Evidence of volume decreasing chemical reactions was also observed in the ultrafast dynamic ellipsometry data for phenylacetylene and acrylonitrile. The liquid 1,3-cyclohexadiene exhibited volume decreasing reaction in the ultrafast dynamic ellipsometry data but did not exhibit an increase in the transient absorption spectra. There was no evidence of chemical reaction in cyclohexane, cyclohexene, benzene, water, acetonitrile, or tert-butylacetylene in the first 350 ps, despite the application of shock stress that was in many cases well above the reaction threshold observed at microsecond time scales.

  19. Various applications of Zeeman atomic absorption spectroscopy

    Koizumi, H.

    1978-06-01

    The application of the Zeeman effect to atomic absorption spectroscopy has been studied over the past several years. This technique has a larger area of application than conventional AAS because of its high degree of selectivity. The ZAA technique can be used for organometallic species determination by interfacing with a high-pressure liquid chromatograph. Various kinds of eluents can be directly introduced in the ZAA system; even organic solvents or high-concentration salt solutions. For example, the Co atom in the functional center of Vitamin B12 molecule was separately analyzed in the presence of much larger amounts of inorganic Co. In the ZAA technique, interference caused by direct spectral overlap can also be corrected. As a typical example, the Sb line at 217.02 nm overlaps the Pb absorption line at 217.00 nm. However, 1000 ppM of Pb did not cause any interference signal in the Sb analysis by ZAA. This is especially important in the analysis of gun powder residue that is often carried out by chemists working in the forensic field. In the determination of trace elements in matrices of unknown composition, the ZAA technique achieved highly reliable results by employing the standard addition method to correct for chemical interferences, because any nonspecific absorption or emission does not give rise to interference signals with this technique.

  20. Symmetry Breaking in Platinum Acetylide Chromophores Studied by Femtosecond Two-Photon Absorption Spectroscopy

    2014-02-01

    The 1PA spectrum in toluene (solid line, top and right axes) and NLT of blank sample (filled black diamonds ) are shown for comparison. The Journal of...G.W., and M.D. ■ REFERENCES (1) Guha, S.; Frazier, C. C.; Porter , P. L.; Kang, K.; Finberg, S. E. Measurement of the 3rd-Order Hyperpolarizability of Pt...Poly-Ynes. Opt. Lett. 1989, 14, 952−954. (2) Guha, S.; kang, K.; Porter , P. L. Two-Photon Absorption-Induced Thermal Effects in Platinum Poly-Ynes

  1. A study of structural differences between TBM patients' and non-TBM persons' CSF using UV-Vis absorption spectroscopy

    Xu, Fangcheng; Wang, Xin; Xu, Huajia; Wang, Kai

    2016-01-01

    Tuberculous meningitis (TBM) is a very common infectious disease in the central nervous system. The delay of diagnosing and treating TBM will lead to high disability and mortality of TBM. Hence, it is very important to promptly diagnose TBM early. In this work, we proposed a new method for diagnosing TBM with CSF samples by using UV-Vis absorption spectroscopy. CSF samples from TBM patients and non-TBM persons were compared, and the sensitivity, specificity, accuracy, positive predictive value reached 83.6%, 69.8%, 77.2%, 76.1% respectively. Our work indicated investigation of CSF using UV-Vis absorption spectroscopy might become a potentially useful method for TBM diagnosis.

  2. Pulse laser photolysis of aqueous ozone in the microsecond range studied by time-resolved far-ultraviolet absorption spectroscopy.

    Goto, Takeyoshi; Morisawa, Yusuke; Higashi, Noboru; Ikehata, Akifumi; Ozaki, Yukihiro

    2013-05-01

    Chemical dynamics of an ozone (O3) pulse-photolytic reaction in aqueous solutions were studied with pump-probe transient far-ultraviolet (FUV) absorption spectroscopy. With a nanosecond pulse laser of 266 nm as pump light, transient spectra of O3 aqueous solutions (78-480 μM, pH 2.5-11.3) were acquired in the time range from -50 to 50 μs in the wavelength region from 190 to 225 nm. The measured transient spectra were linearly decomposed into the molar absorption coefficients and the concentration-time profiles of constituted chemical components with a multivariate curve resolution method. From the dependences of the time-averaged concentrations for 20 μs of the constituted chemicals on the initial concentration of O3, it was found that the transient spectra involve the decomposition of O3 and the formation of hydrogen peroxide (H2O2) and a third component that is assigned to hydroxyl radical (OH) or perhydroxyl radical (HO2). Furthermore, the pH dependence of the time-averaged concentration of the third components indicates that HO2 is more probable than OH as the third component. The time-averaged concentration ratio of each chemical component to the initial O3 concentration depends on the pH conditions from -0.95 to -0.60 for O3, 0.98 to 1.2 for H2O2, 0.002 to 0.29 for OH, and 0.012 to 0.069 for HO2.

  3. Gold/titania composites: An X-ray absorption spectroscopy study on the influence of the reduction method

    Meire, Mieke [Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281-S3, 9000 Ghent (Belgium); Tack, Pieter [Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, 9000 Ghent (Belgium); De Keukeleere, Katrien [Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281-S3, 9000 Ghent (Belgium); Balcaen, Lieve [Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, 9000 Ghent (Belgium); Pollefeyt, Glenn [Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281-S3, 9000 Ghent (Belgium); Vanhaecke, Frank; Vincze, Laszlo [Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, 9000 Ghent (Belgium); Van Der Voort, Pascal; Van Driessche, Isabel [Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281-S3, 9000 Ghent (Belgium); Lommens, Petra, E-mail: Petra.Lommens@UGent.be [Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2015-08-01

    The functionalization of titania based materials with noble metal cocatalysts such as gold or platinum is a well known procedure to improve the catalytic activity of these materials in for example the degradation of organic pollutants or CO conversion. Parameters such as cocatalyst load, noble metal particle size and oxidation state influence the efficiency of these materials. We have impregnated a mesoporous titania powder with a gold salt and used different synthesis routes to reduce the gold ions. A structural analysis was performed using electron microscopy and nitrogen sorption. An X-ray absorption near edge structure spectroscopy study, in both high and low resolution, was performed to investigate the influence of the different reduction methods on the oxidation state of the gold atoms. This technique can also provide information on the local environment of the gold atoms and their interaction with the titanium dioxide host. We found that varying the reduction method has a significant impact on the oxidation state of the gold cocatalysts. This lead to varying interactions with the titania support and charging of the gold nanoparticles. - Highlights: • Influence of reduction method on Au/TiO{sub 2} was studied. • Hydrogen reduction of gold salt results in the smallest particles of 2.4 nm. • XANES is used to determine the oxidation state of gold atoms. • Hydrogen and microwave synthesis produce completely reduced gold particles. • UV reduction of gold salt leads to positively charged particles.

  4. Local structure studies of Fe2TeO6 using x-ray absorption spectroscopy

    Singh, Harishchandra; Yadav, A. K.

    2016-05-01

    In the present study, we have performed EXAFS measurements on powder samples of Fe2TeO6 (FTO) to probe the local structure surrounding at the Fe site. The structural parameters (atomic coordination and lattice parameters) of FTO used for simulation of theoretical EXAFS spectra of the samples have been obtained from Rietveld refined structure on synchrotron X-ray Diffraction (SXRD) data. Quite similar and satisfactory structural parameters have been obtained from both the study, indicating goodness of synchrotron structural analysis over EXAFS analysis. SXRD and EXAFS results shows absence of any secondary phase proves current synthesis superior over reported techniques.

  5. Gold/titania composites: An X-ray absorption spectroscopy study on the influence of the reduction method

    Meire, Mieke; Tack, Pieter; De Keukeleere, Katrien; Balcaen, Lieve; Pollefeyt, Glenn; Vanhaecke, Frank; Vincze, Laszlo; Van Der Voort, Pascal; Van Driessche, Isabel; Lommens, Petra

    2015-08-01

    The functionalization of titania based materials with noble metal cocatalysts such as gold or platinum is a well known procedure to improve the catalytic activity of these materials in for example the degradation of organic pollutants or CO conversion. Parameters such as cocatalyst load, noble metal particle size and oxidation state influence the efficiency of these materials. We have impregnated a mesoporous titania powder with a gold salt and used different synthesis routes to reduce the gold ions. A structural analysis was performed using electron microscopy and nitrogen sorption. An X-ray absorption near edge structure spectroscopy study, in both high and low resolution, was performed to investigate the influence of the different reduction methods on the oxidation state of the gold atoms. This technique can also provide information on the local environment of the gold atoms and their interaction with the titanium dioxide host. We found that varying the reduction method has a significant impact on the oxidation state of the gold cocatalysts. This lead to varying interactions with the titania support and charging of the gold nanoparticles.

  6. Surface study of metal-containing ionic liquids by means of photoemission and absorption spectroscopies

    Caporali, Stefano; Pedio, Maddalena; Chiappe, Cinzia; Pomelli, Christian S.; Acres, Robert G.; Bardi, Ugo

    2016-06-01

    The vacuum/liquid interface of different ionic liquids obtained by dissolving bistriflimide salts of Ag, Al, Cu, Ni, and Zn in 1-butyl-3-methylimidazolium bistriflimide ([bmim][Tf2N]) was investigated under vacuum using AR-XPS and NEXAFS. The XPS spectra show chemical shifts of the nitrogen of the bistriflimide anion as a function of the metal type, indicating different strength of the coordination bonds. In silver bearing ILs, silver ions were found to be only weakly coordinated. On the contrary, Ni, Cu, Zn, and especially Al exhibit large chemical shifts attributable to strong interaction with the bistriflimide ions. The outermost surface was enriched with or depleted of metal ions as a function of the nature of the metals. Nickel and zinc tend to slightly concentrate at the surface while copper, silver, and especially aluminum are depleted at the surface. We also observed that the aliphatic alkyl chains of the cations tend to protrude outside the surface in all systems studied. However, the presence of metals generally increases the amount of bistriflimide at the vacuum/liquid interface.

  7. Triplet absorption spectroscopy and electromagnetically induced transparency

    Ghafoor, F.; Nazmitdinov, R. G.

    2016-09-01

    Coherence phenomena in a four-level atomic system, cyclically driven by three coherent fields, are investigated thoroughly at zero and weak magnetic fields. Each strongly interacting atomic state is converted to a triplet due to a dynamical Stark effect. Two dark lines with a Fano-like profile arise in the triplet absorption spectrum with anomalous dispersions. We provide conditions to control the widths of the transparency windows by means of the relative phase of the driving fields and the intensity of the microwave field, which closes the optical system loop. The effect of Doppler broadening on the results of the triplet absorption spectroscopy is analysed in detail.

  8. X-ray photoelectron spectroscopy study of pyrolytically coated graphite platforms submitted to simulated electrothermal atomic absorption spectrometry conditions

    Ruiz, Frine [Laboratorio de Quimica Analitica, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela); Benzo, Zully [Laboratorio de Quimica Analitica, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela); Quintal, Manuelita [Laboratorio de Quimica Analitica, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela); Garaboto, Angel [Laboratorio de Quimica Analitica, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela); Albornoz, Alberto [Laboratorio de Fisicoquimica de Superficies, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela); Brito, Joaquin L. [Laboratorio de Fisicoquimica de Superficies, Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado Postal 21827, Caracas 1020-A (Venezuela)]. E-mail: joabrito@ivic.ve

    2006-10-15

    The present work is part of an ongoing project aiming to a better understanding of the mechanisms of atomization on graphite furnace platforms used for electrothermal atomic absorption spectrometry (ETAAS). It reports the study of unused pyrolytic graphite coated platforms of commercial origin, as well as platforms thermally or thermo-chemically treated under simulated ETAAS analysis conditions. X-ray photoelectron spectroscopy (XPS) was employed to study the elements present at the surfaces of the platforms. New, unused platforms showed the presence of molybdenum, of unknown origin, in concentrations up to 1 at.%. Species in two different oxidations states (Mo{sup 6+} and Mo{sup 2+}) were detected by analyzing the Mo 3d spectral region with high resolution XPS. The analysis of the C 1s region demonstrated the presence of several signals, one of these at 283.3 eV related to the presence of Mo carbide. The O 1s region showed also various peaks, including a signal that can be attributed to the presence of MoO{sub 3}. Some carbon and oxygen signals were consistent with the presence of C=O and C-O- (probably C-OH) groups on the platforms surfaces. Upon thermal treatment up to 2900 deg. C, the intensity of the Mo signal decreased, but peaks due to Mo oxides (Mo{sup 6+} and Mo{sup 5+}) and carbide (Mo{sup 2+}) were still apparent. Thermo-chemical treatment with 3 vol.% HCl solutions and heating up to 2900 deg. C resulted in further diminution of the Mo signal, with complete disappearance of Mo carbide species. Depth profiling of unused platforms by Ar{sup +} ion etching at increasing time periods demonstrated that, upon removal of several layers of carbonaceous material, the Mo signal disappears suggesting that this contamination is present only at the surface of the pyrolytic graphite platform.

  9. Speciation of zinc in municipal solid waste incineration fly ash after heat treatment: an X-ray absorption spectroscopy study.

    Struis, Rudolf P W J; Ludwig, Christian; Lutz, Harald; Scheidegger, André M

    2004-07-01

    Fly ash is commonly deposited in special landfills as it contains toxic concentrations of heavy metals, such as Zn, Pb, Cd, and Cu. This study was inspired by our efforts to detoxify fly ash from municipal solid waste incineration by thermal treatment to produce secondary raw materials suited for reprocessing. The potential of the thermal treatment was studied by monitoring the evaporation rate of zinc from a certified fly ash (BCR176) during heating between 300 and 950 degrees C under different carrier gas compositions. Samples were quenched at different temperatures for subsequent investigation with X-ray absorption spectroscopy (XAS). The XAS spectra were analyzed using principal component analysis (PCA), target transformation (TT), and linear combination fitting (LCF) to analyze the major Zn compounds in the fly ash as a function of the temperature. The original fly ash comprised about 60% zinc oxides mainly in the form of hydrozincite (Zn5(OH)6(CO3)2) and 40% inerts like willemite (Zn2SiO4) and gahnite (ZnAl2O4) in a weight ratio of about 3:1. At intermediate temperatures (550-750 degrees C) the speciation underlines the competition between indigenous S and Cl with solid zinc oxides to form either volatile ZnCl2 or solid ZnS. ZnS then transformed into volatile species at about 200 degrees C higher temperatures. The inhibiting influence of S was found absent when oxygen was introduced to the inert carrier gas stream or chloride-donating alkali salt was added to the fly ash.

  10. Photothermal deflection spectroscopy for the study of thin films and optical coatings: measurements of absorption losses and detection of photoinduced changes

    Commandre, Mireille; Roche, Pierre J.; Albrand, Gerard; Pelletier, Emile P.

    1990-08-01

    Photothermal deflection has been used to map the absorption characteristics of thin film optical coatings. Our experimental set-up can give low level absorption coefficient down to 1 ppm, with a spatial resolution limited by the excitating laser beam diameter (100 tim). On single layer films, we can calculate extinction coefficient of the deposited material with a detectivity of a few i07. We present a study of absorption losses in single layer titania films and in TiOWSiO2 Fabry-Perot filters prepared in our laboratory by electron beam evaporation, ion assisted deposition and ion plating. Local variations of absorption on the sample surface can be very large especially in lowly absorbing samples; high absorption sites may be related to local defects responsible for laser damage. Furthermore, we show that some titania films can present photoinduced instabilities. Photothermal deflection spectroscopy is a good way to study absorption evolution under illumination. In Ti02/Si02 Fabry-Perot filters, we have observed that these absorption changes are associated with important drifts of transmission curves. So these instabilities can be explained by a change of the value of the complex index Ii = n - ik. Results lead to the conclusion that stability under illumination is strongly correlated to the deposition technique and also to the deposition conditions: unstable samples are mostly prepared by electron beam evaporation.

  11. Emission and absorption spectroscopy study of Ar excited states in 13.56 MHz argon plasma operating at sub-atmospheric to atmospheric pressure

    Li, L. [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Jozef Plateaustraat 22, Ghent B-9000 (Belgium); Nikiforov, A., E-mail: anton.nikiforov@ugent.be [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Jozef Plateaustraat 22, Ghent B-9000 (Belgium); Institute of Solution Chemistry of the Russian Academy of Science, Academicheskaya St., 1, Ivanovo, 153045 (Russian Federation); Britun, N. [Chimie des Interactions Plasma-Surface (ChIPS), CIRMAP, Universite de Mons, 23 Place du Parc, B-7000 Mons (Belgium); Snyders, R. [Chimie des Interactions Plasma-Surface (ChIPS), CIRMAP, Universite de Mons, 23 Place du Parc, B-7000 Mons (Belgium); Materia Nova Research Centre, Parc Initialis, B-7000 Mons (Belgium); Leys, C. [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Jozef Plateaustraat 22, Ghent B-9000 (Belgium)

    2015-05-01

    The densities of metastable and resonant states of Ar atoms are measured in high pressure Ar radio frequency discharge. Resonant absorption spectroscopy for the case of a low pressure spectral lamp and high-pressure plasma absorption lines is implemented for this purpose. The necessary generalizations for the high-pressure resonant absorption method are given. Absolute density of Ar 1s levels obtained at different RF input power and operating pressures are of the order of 10{sup 11} cm{sup −3}, which is in a good agreement with those reported in the literature. The population distribution on the Ar 2p (excited) levels, obtained from the optical emission spectroscopy, reveals strong deviation from thermal equilibrium for these levels in the high-pressure case. The generation of the Ar excited states in the studied discharges is compared to the previously reported results. - Highlights: • Strong non-equilibrium distribution of Ar 2p levels is observed. • The absolute number density of non-radiative Ar 1s states is determined by the easier and low cost spectral-lamp absorption method. • The modified absorption theory of Mitchell and Zemanski was used to obtain the absolute number density of Ar 1s states at high pressure. • The developed RF source with 5 cm long gap can be a possible alternative to micro-plasma working in Ar at atmospheric pressure.

  12. Complexation of lactate with neodymium(III) and europium(III) at variable temperatures: studies by potentiometry, microcalorimetry, optical absorption, and luminescence spectroscopy.

    Tian, Guoxin; Martin, Leigh R; Rao, Linfeng

    2010-11-15

    The complexation of neodymium(III) and europium(III) with lactate was studied at variable temperatures by potentiometry, absorption spectrophotometry, luminescence spectroscopy, and microcalorimetry. The stability constants of three successive lactate complexes (ML(2+), ML(2)(+), and ML(3)(aq), where M stands for Nd and Eu and L stands for lactate) at 10, 25, 40, 55, and 70 °C were determined. The enthalpies of complexation at 25 °C were determined by microcalorimetry. Thermodynamic data show that the complexation of trivalent lanthanides (Nd(3+) and Eu(3+)) with lactate is exothermic and the complexation becomes weaker at higher temperatures. Results from optical absorption and luminescence spectroscopy suggest that the complexes are inner-sphere chelate complexes in which the protonated α-hydroxyl group of lactate participates in the complexation.

  13. Cavity-Enhanced Ultrafast Transient Absorption Spectroscopy

    Reber, Melanie A R; Allison, Thomas K

    2015-01-01

    We present a new technique using a frequency comb laser and optical cavities for performing ultrafast transient absorption spectroscopy with improved sensitivity. Resonantly enhancing the probe pulses, we demonstrate a sensitivity of $\\Delta$OD $ = 1 \\times 10^{-9}/\\sqrt{\\mbox{Hz}}$ for averaging times as long as 30 s per delay point ($\\Delta$OD$_{min} = 2 \\times 10^{-10}$). Resonantly enhancing the pump pulses allows us to produce a high excitation fraction at high repetition-rate, so that signals can be recorded from samples with optical densities as low as OD $\\approx 10^{-8}$, or column densities $< 10^{10}$ molecules/cm$^2$. This high sensitivity enables new directions for ultrafast spectroscopy.

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

    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…

  15. Absorption spectroscopy of EBT model GAFCHROMIC film.

    Devic, Slobodan; Tomic, Nada; Pang, Zhiyu; Seuntjens, Jan; Podgorsak, Ervin B; Soares, Christopher G

    2007-01-01

    The introduction of radiochromic films has solved some of the problems associated with conventional 2D radiation detectors. Their high spatial resolution, low energy dependence, and near-tissue equivalence make them ideal for measurement of dose distributions in radiation fields with high dose gradients. Precise knowledge of the absorption spectra of these detectors can help to develop more suitable optical densitometers and potentially extend the use of these films to other areas such as the measurement of the radiation beam spectral information. The goal of this study is to present results of absorption spectra measurements for the new GAFCHROMIC film, EBT type, exposed to 6 MV photon beam in the dose range from 0 to 6 Gy. Spectroscopic analysis reveals that in addition to the two main absorption peaks, centered at around 583 and 635 nm, the absorption spectrum in the spectral range from 350 to 800 nm contains six more absorption bands. Comparison of the absorption spectra reveals that previous HD-810, MD-55, as well as HS GAFCHROMIC film models, have nearly the same sensitive layer base material, whereas the new EBT model, GAFCHROMIC film has a different composition of its sensitive layer. We have found that the two most prominent absorption bands in EBT model radiochromic film do not change their central wavelength position with change in a dose deposited to the film samples.

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

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

    2015-06-01

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

  17. A comparative study on the ionic liquid [bmim][BF4] and its solution with transient absorption spectroscopy.

    Zhu, Guanglai; Wu, Guozhong; Xu, Xinsheng; Ji, Xuehan

    2011-11-01

    A detailed study was explored to compare the transient absorption spectra of the neat 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) with its solution in water or acetonitrile. It was concluded that the excited triplet state (3)[bmim](+*) was produced after 266 nm laser irradiation, and then the neutral radical [bmim] and the cation radical [bmim] (2+) were formed through two possible paths. The transient absorption spectra of the neat [bmim][BF(4)] and its solution were similar but the reaction kinetics were different due to their different local structures such as dimeric or cluster. The energy transfer between excited [bmim][BF(4)] and β-carotene further affirmed the existence of (3)[bmim](+*). And the reaction that the hydrated electron captured by [bmim](+) to produce [bmim] in solution was observed.

  18. X-ray absorption spectroscopy and magnetic circular dichroism studies of L10-Mn-Ga thin films

    Glas, M.; Sterwerf, C.; Schmalhorst, J. M.; Ebke, D.; Jenkins, C.; Arenholz, E.; Reiss, G.

    2013-11-01

    Tetragonally distorted Mn3-xGax thin films with 0.1magnetic anisotropy and low magnetization and thus have the potential to serve as electrodes in spin transfer torque magnetic random access memory. Because a direct capping of these films with MgO is problematic due to oxide formation, we examined the influence of a CoFeB interlayer and of two different deposition methods for the MgO barrier on the formation of interfacial Mn-O for Mn62Ga38 by element specific X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). A highly textured L10 crystal structure of the Mn-Ga films was verified by X-ray diffraction measurements. For samples with e-beam evaporated MgO barrier no evidence for Mn-O was found whereas in samples with magnetron sputtered MgO, Mn-O was detected, even for the thickest interlayer thickness. Both XAS and XMCD measurements showed an increasing interfacial Mn-O amount with decreasing CoFeB interlayer thickness. Additional element specific full hysteresis loops determined an out-of-plane magnetization axis for the Mn and Co, respectively.

  19. X-ray absorption spectroscopy and magnetic circular dichroism studies of L1{sub 0}-Mn-Ga thin films

    Glas, M., E-mail: mglas@physik.uni-bielefeld.de; Sterwerf, C.; Schmalhorst, J. M.; Reiss, G. [Thin Films and Physics of Nanostructures, Bielefeld University, Bielefeld (Germany); Ebke, D. [Thin Films and Physics of Nanostructures, Bielefeld University, Bielefeld (Germany); Max Planck Institute for Chemical Physics of Solids, Dresden (Germany); Jenkins, C.; Arenholz, E. [ALS Berkeley, California 94720-8229 (United States)

    2013-11-14

    Tetragonally distorted Mn{sub 3−x}Ga{sub x} thin films with 0.1absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). A highly textured L1{sub 0} crystal structure of the Mn-Ga films was verified by X-ray diffraction measurements. For samples with e-beam evaporated MgO barrier no evidence for Mn-O was found whereas in samples with magnetron sputtered MgO, Mn-O was detected, even for the thickest interlayer thickness. Both XAS and XMCD measurements showed an increasing interfacial Mn-O amount with decreasing CoFeB interlayer thickness. Additional element specific full hysteresis loops determined an out-of-plane magnetization axis for the Mn and Co, respectively.

  20. Tomographic x-ray absorption spectroscopy.

    Schroer, C. G.; Kuhlmann, M.; Gunzler, T. F.; Lengeler, B.; Richwin, M.; Griesebock, B.; Lutzenkirchen-Hecht, D.; Frahm, R.; Ziegler, E.; Mashayekhi, A.; Haeffner, D. R.; Grunwaldt, J. -D.; Baiker, A.; Experimental Facilities Division (APS); Aachen Univ.; HASYLAB at DESY; Bergische Univ. Wuppertal; ESRF; Inst. for Chemical and Bioengineering

    2004-01-01

    Hard x-ray absorption spectroscopy is combined with scanning microtomography to reconstruct full near edge spectra of an elemental species at each point on an arbitrary virtual section through a sample. These spectra reveal the local concentration of different chemical compounds of the absorbing element inside the sample and give insight into the oxidation state and the local projected free density of states. The method is implemented by combining a quick scanning monochromator and data acquisition system with a scanning microprobe setup based on refractive x-ray lenses. The full XANES spectra reconstructed at each point of the tomographic slice allow one to detect slight variations in concentration of the chemical compounds, such as Cu and Cu(I){sub 2}O.

  1. X-ray absorption spectroscopy of semiconductors

    Ridgway, Mark

    2015-01-01

    X-ray Absorption Spectroscopy (XAS) is a powerful technique with which to probe the properties of matter, equally applicable to the solid, liquid and gas phases. Semiconductors are arguably our most technologically-relevant group of materials given they form the basis of the electronic and photonic devices that now so widely permeate almost every aspect of our society. The most effective utilisation of these materials today and tomorrow necessitates a detailed knowledge of their structural and vibrational properties. Through a series of comprehensive reviews, this book demonstrates the versatility of XAS for semiconductor materials analysis and presents important research activities in this ever growing field. A short introduction of the technique, aimed primarily at XAS newcomers, is followed by twenty independent chapters dedicated to distinct groups of materials. Topics span dopants in crystalline semiconductors and disorder in amorphous semiconductors to alloys and nanometric material as well as in-sit...

  2. Highly sensitive detection using Herriott cell for laser absorption spectroscopy

    Zhao, Chongyi; Song, Guangming; Du, Yang; Zhao, Xiaojun; Wang, Wenju; Zhong, Liujun; Hu, Mai

    2016-11-01

    The tunable diode laser absorption spectroscopy combined with the long absorption path technique is a significant method to detect harmful gas. The long optical path could come true by Herriott cell reducing the size of the spectrometers. A 15 cm long Herriott cell with 28.8 m optical absorption path after 96 times reflection was designed that enhanced detection sensitivity of absorption spectroscopy. According to the theory data of calculation, Herriott cell is analyzed and simulated by softwares Matlab and Lighttools.

  3. Study of some Ayurvedic Indian medicinal plants for the essential trace elemental contents by instrumental neutron activation analysis and atomic absorption spectroscopy techniques

    Lokhande, R.S.; Singare, P.U.; Andhele, M.L. [Dept. of Chemistry, Univ. of Mumbai, Santacruz, Mumbai (India); Acharya, R.; Nair, A.G.C.; Reddy, A.V.R. [Radiochemistry Div., Bhabha Atomic Research Centre, Trombay, Mumbai (India)

    2009-07-01

    Elemental analysis of some medicinal plants used in the Indian Ayurvedic system was performed by employing instrumental neutron activation analysis (INAA) and atomic absorption spectroscopy (AAS) techniques. The samples were irradiated with thermal neutrons in a nuclear reactor and the induced activity was counted by gamma ray spectrometry using an efficiency calibrated high resolution high purity germanium (HPGe) detector. Most of the medicinal plants were found to be rich in one or more of the elements under study. The variation in elemental concentration in same medicinal plants samples collected in summer, winter and rainy seasons was studied and the biological effects of these elements on human beings are discussed. (orig.)

  4. Infrared absorption spectroscopy and chemical kinetics of free radicals

    Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

    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.

  5. Where Do Photogenerated Holes Go in Anatase:Rutile TiO2? A Transient Absorption Spectroscopy Study of Charge Transfer and Lifetime.

    Kafizas, Andreas; Wang, Xiuli; Pendlebury, Stephanie R; Barnes, Piers; Ling, Min; Sotelo-Vazquez, Carlos; Quesada-Cabrera, Raul; Li, Can; Parkin, Ivan P; Durrant, James R

    2016-02-11

    Anatase:rutile TiO2 junctions are often shown to be more photocatalytically active than anatase or rutile alone, but the underlying cause of this improvement is not fully understood. Herein, we employ transient absorption spectroscopy to study hole transfer across the anatase:rutile heterojunction in films as a function of phase composition. By exploiting the different signatures in the photoinduced absorption of trapped charges in anatase and rutile, we were able to separately track the yield and lifetime of holes in anatase and rutile sites within phase composites. Photogenerated holes transfer from rutile to anatase on submicrosecond time scales. This hole transfer can significantly increase the anatase hole yield, with a 20:80 anatase:rutile composite showing a 5-fold increase in anatase holes observed from the microsecond. Hole transfer does not result in an increase in charge-carrier lifetime, where an intermediate recombination dynamic between that of pure anatase (t1/2 ≈ 0.5 ms) and rutile (t1/2 ≈ 20 ms) is found in the anatase:rutile junction (t1/2 ≈ 4 ms). Irrespective of what the formal band energy alignment may be, we demonstrate the importance of trap-state energetics for determining the direction of photogenerated charge separation across heterojunctions and how transient absorption spectroscopy, a method that can specifically track the migration of trapped charges, is a useful tool for understanding this behavior.

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

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

    2016-09-08

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

  7. Monitoring a CuO gas sensor at work: an advanced in situ X-ray absorption spectroscopy study.

    Volanti, D P; Felix, A A; Suman, P H; Longo, E; Varela, J A; Orlandi, M O

    2015-07-28

    X-ray absorption near edge structure (XANES) and electrical measurements were used to elucidate the local structure and electronic changes of copper(II) oxide (CuO) nanostructures under working conditions. For this purpose, a sample holder layout was developed enabling the simultaneous analysis of the spectroscopic and electrical properties of the sensor material under identical operating conditions. The influence of different carrier gases (e.g., air and N2) on the CuO nanostructures behavior under reducing conditions (H2 gas) was studied to analyze how a particular gas atmosphere can modify the oxidation state of the sensor material in real time.

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

    Sigircik, Gokmen, E-mail: gsigircik@cu.edu.tr [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Erken, Ozge [Department of Physics, Faculty Science and Letters, Adiyaman University, 02040 Adiyaman (Turkey); Tuken, Tunc [Chemistry Department, University of Cukurova, 01330 Adana (Turkey); Gumus, Cebrail [Physics Department, University of Cukurova, 01330 Adana (Turkey); Ozkendir, Osman M. [Department of Energy Systems Engineering Tarsus Technology Faculty, Mersin University, 33400 Tarsus (Turkey); Ufuktepe, Yuksel [Physics Department, University of Cukurova, 01330 Adana (Turkey)

    2015-06-15

    Highlights: • Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. • Uniform and well-defined ZnO nano-towers and rods have been obtained via electrochemical deposition. • The presence of chloride ions altered the nucleation rate of ZnO particles on ITO substrates and resulting crystallographic properties. • Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valance band electrons is different. - Abstract: Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn{sup 2+} and OH{sup −}) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (T{sub c}) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated E{sub g} values are in the range 3.28–3.41 eV and 3.22–3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm{sup 2} V{sup −1} s{sup −1} and 126.2 to 204.7 cm{sup 2} V{sup −1} s{sup −1} for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K

  9. A new Differential Optical Absorption Spectroscopy instrument to study atmospheric chemistry from a high-altitude unmanned aircraft

    Stutz, Jochen; Werner, Bodo; Spolaor, Max; Scalone, Lisa; Festa, James; Tsai, Catalina; Cheung, Ross; Colosimo, Santo F.; Tricoli, Ugo; Raecke, Rasmus; Hossaini, Ryan; Chipperfield, Martyn P.; Feng, Wuhu; Gao, Ru-Shan; Hintsa, Eric J.; Elkins, James W.; Moore, Fred L.; Daube, Bruce; Pittman, Jasna; Wofsy, Steven; Pfeilsticker, Klaus

    2017-03-01

    Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14-18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301-387 nm), visible (410-525 nm), and near infrared (900-1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O3, O4, NO2, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O4 observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O4 SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O3 observations overcomes this issue. Extensive sensitivity calculations show that the novel O3-scaling technique allows the retrieval of BrO and NO2 mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO2 mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS.

  10. Absorption/emission spectroscopy and applications using shock tubes

    Sulzmann, K. G. P.

    1988-09-01

    A historical overview is presented about the important contributions made by Penner, his co-workers, and his students to the application of shock-tube techniques for quantitative emission and absorption spectroscopy and its applications to chemical kinetics studies in high-temperature gases. The discussions address critical aspects related to valid determinations of quantitative spectroscopic data and chemical rate parameters and stress the requirements for uniformly heated gas samples, temperature determinations, gas-mixture preparations, selection of useful spectral intervals, verification of LTE conditions, time resolutions for concentration histories, uniqueness of kinetic measurements, as well as accuracies and reproducibilities of measurement results.The potential of absorption spectroscopy by molecule and/or radical resonance radiation and by laser transmission techniques is highlighted for kinetic studies in mixtures with very small reactant concentrations.Besides the work by the honoree and his school, the references include books, monographs and key articles related to the subjects discussed.

  11. Vacuum ultraviolet absorption spectroscopy in combination with comprehensive two-dimensional gas chromatography for the monitoring of volatile organic compounds in breath gas: A feasibility study.

    Gruber, Beate; Groeger, Thomas; Harrison, Dale; Zimmermann, Ralf

    2016-09-16

    Vacuum ultraviolet (VUV) absorption spectroscopy was recently introduced as a new detection system for one, as well as comprehensive two-dimensional gas chromatography (GC×GC) and successfully applied to the analysis of various analytes in several matrices. In this study, its suitability for the analysis of breath metabolites was investigated and the impact of a finite volume of the absorption cell and makeup gas pressure was evaluated for volatile analytes in terms of sensitivity and chromatographic resolution. A commercial available VUV absorption spectrometer was coupled to GC×GC and applied to the analysis of highly polar volatile organic compounds (VOCs). Breath gas samples were acquired by needle trap micro extraction (NTME) during a glucose challenge and analysed by the applied technique. Regarding qualitative and quantitative information, the VGA-100 is compatible with common GC×GC detection systems like FID and even TOFMS. Average peak widths of 300ms and LODs in the lower ng range were achieved using GC×GC-VUV. Especially small oxygenated breath metabolites show intense and characteristic absorption patterns in the VUV region. Challenge responsive VOCs could be identified and monitored during a glucose challenge. The new VUV detection technology might especially be of benefit for applications in clinical research.

  12. Femtosecond broadband absorption spectroscopy of photodissociating molecules

    Glownia, J.; Misewich, J.; Walkup, R.; Kaschke, M.; Sorokin, P.; Schäfer, F. P.; Walther, H.; Shin, S. K.; Chen, Y.; Böhmer, E.; Wittig, C.; Magni, V.; De Silvestri, S.; Cybo-Ottone, A.; Nisoli, M.; Svelto, O.; Bor, Z.; Horváth, Z. L.; Elsaesser, T.; Kaiser, W.; Wilhelmi, B.; Szatmári, S.; Tittel, F. K.; Hofmann, T.; Sharp, T. E.; Wisoff, P. J.; Wilson, W. L.; Szabó, G.; Letokhov, V. S.; Beutel, V.; Bhale, G.; Demtröder, W.; Eckel, H.-A.; Gress, J.; Kuhn, M.; Richter, W.; Svanberg, S.; Neusser, H. J.; Riedel, E.; Weber, T.; Schlag, E. W.; Kuhl, J.; Klingenstein, M.; Lambsdorff, M.; Rosenzweig, J.; Moglestue, C.; Axmann, A.; von der Linde, D.; zu Putlitz, G.; R. Beau, M.

    We have tried to present a picture of what is conceptually involved in our studies thus far. The major finding has been the observation that two widely different types of transient absorption spectra are to be seen in nature, the type we call "impact spectra", and the type we term "statistical spectra". Both types, when interpreted and analyzed properly, can provide information about difference potentials.

  13. Applications of absorption spectroscopy using quantum cascade lasers.

    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.

  14. [Digestion-flame atomic absorption spectroscopy].

    Xu, Liang; Hu, Jian-Guo; Liu, Rui-Ping; Wang, Zhi-Min; Narenhua

    2008-01-01

    A microwave digestion-flame atomic absorption spectroscopy (FAAS) method was developed for the determination of metal elements Na, Zn, Cu, Fe, Mn, Ca and Mg in Mongolian patents. The instrument parameters for the determination were optimized, and the appropriate digestion solvent was selected. The recovery of the method was between 95.8% and 104.3%, and the RSD was between 1.6% and 4.2%. The accuracy and precision of the method was tested by comparing the values obtained from the determination of the standard sample, bush twigs and leaves (GSV-1) by this method with the reference values of GSV-1. The determination results were found to be basically consistent with the reference values. The microwave digestion technique was applied to process the samples, and the experimental results showed that compared to the traditional wet method, the present method has the merits of simplicity, saving agents, rapidness, and non-polluting. The method was accurate and reliable, and could be used to determine the contents of seven kinds of metal elements in mongolian patents.

  15. An experimental set-up to apply polarization modulation to infrared reflection absorption spectroscopy for improved in situ studies of atmospheric corrosion processes.

    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.

  16. [Study of pH measuring based on i-motif DNA conformation switch and UV-Vis absorption spectroscopy of gold nanoparticles].

    Zhong, Jian-hai; Guo, Liang-qia; Wu, Jin-mei; Chen, Jin-feng; Chen, Zhang-jie

    2012-04-01

    A fast, sensitive, colorimetric method for the detection of pH based on the differentiate effect of gold nanoparticles to the configuration of DNA was developed in this study. The UV-Vis absorption spectroscopy of the i-motif DNA-Au NPs system has been investigated, and the effect of the concentration of salt and i-motif DNA, reaction time and DNA sequence on the pH response of the system have been also optimized. Under the optimum conditions, the UV-Vis absorption spectroscopy of the Au NPs is changed regularly with pH in the range of 5.3 - 7.0, the absorbance at 520 nm is increased gradually while at 700 nm decreased. Correspondingly, the color of the Au NPs is varied from violet to red. The pH sensor is no need to modification, low cost, fast and can be carried out by naked eyes. It is promising to use in monitoring some life process which associated with pH variation.

  17. UV-VIS absorption spectroscopy: Lambert-Beer reloaded

    Mäntele, Werner; Deniz, Erhan

    2017-02-01

    UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems.

  18. Study of the contact charge transfer behavior between cryptophanes (A and E) and fullerene by absorption, fluorescence and {sup 1}H NMR spectroscopy

    Zhang Caihong; Shen Weili; Fan Ruying; Zhang Guomei; Shangguan Lingzhi; Chao Jianbin; Shuang Shaomin [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Dong Chuan, E-mail: dc@sxu.edu.cn [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Choi, Martin M.F., E-mail: mfchoi@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong (Hong Kong)

    2009-09-14

    A group of novel cage-like compounds cryptophanes A and E were synthesized from vanillin by a three-step method. The intermolecular interaction between cryptophanes (A and E) and fullerene (C{sub 60}) was investigated in detail by absorption, fluorescence and {sup 1}H NMR spectroscopy. The absorption of C{sub 60} at 410-650 nm decreased in the presence of cryptophanes A or E. The decrease in absorption intensity was proportional to the concentration of cryptophanes A or E. On the other hand, the fluorescence intensity of cryptophanes A or E decreased and the emission maxima were blue-shifted with the increase in C{sub 60} concentration. These results suggest that contact charge transfer (CCT) complexes can be formed from C{sub 60} with cryptophanes A or E. In addition, the electrochemical behavior of cryptophanes (A and E) and C{sub 60} was studied by cyclic voltammetry. The redox currents of cryptophanes (A and E) decreased and the peak potentials were shifted on addition of C{sub 60}. The changes in the chemical shifts ({Delta}{delta}) of aromatic protons of cryptophanes (A and E) in their NMR spectra further support that CCT complexes were formed with cryptophanes as the electron donors and C{sub 60} as the electron acceptor.

  19. Diode laser absorption spectroscopy of lithium isotopes

    Olivares, Ignacio E.; González, Iván A.

    2016-10-01

    We study Doppler-limited laser intensity absorption, in a thermal lithium vapor containing 7Li and 6Li atoms in a 9 to 1 ratio, using a narrow-linewidth single-longitudinal-mode tunable external cavity diode laser at the wavelength of 670.8 nm. The lithium vapor was embedded in helium or argon buffer gas. The spectral lineshapes were rigorously predicted for D_1 and D_2 for the lithium 6 and 7 isotope lines using reduced optical Bloch equations, specifically derived, from a density matrix analysis. Here, a detailed comparison is provided of the predicted lineshapes with the measured 7Li-D_2, 7Li-D_1, 6Li-D_2 and 6Li-D_1 lines, in the case of high vapor density and with intensity above the saturation intensity. To our knowledge, this is the first time that such detailed comparison is reported in the open literature. The calculations were also extended to saturated absorption spectra and compared to measured Doppler-free 7Li-D_2 and 6Li-D_2 hyperfine lines.

  20. Principles and calibration of collinear photofragmentation and atomic absorption spectroscopy

    Sorvajärvi, Tapio; Toivonen, Juha

    2014-06-01

    The kinetics of signal formation in collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) are discussed, and theoretical equations describing the relation between the concentration of the target molecule and the detected atomic absorption in case of pure and impure samples are derived. The validity of the equation for pure samples is studied experimentally by comparing measured target molecule concentrations to concentrations determined using two other independent techniques. Our study shows that CPFAAS is capable of measuring target molecule concentrations from parts per billion (ppb) to hundreds of parts per million (ppm) in microsecond timescale. Moreover, the possibility to extend the dynamic range to cover eight orders of magnitude with a proper selection of fragmentation light source is discussed. The maximum deviation between the CPFAAS technique and a reference measurement technique is found to be less than 5 %. In this study, potassium chloride vapor and atomic potassium are used as a target molecule and a probed atom, respectively.

  1. Valence-to-core-detected X-ray absorption spectroscopy

    Hall, Eleanor R.; Pollock, Christopher J.; Bendix, Jesper;

    2014-01-01

    X-ray absorption spectroscopy (XAS) can provide detailed insight into the electronic and geometric structures of transition-metal active sites in metalloproteins and chemical catalysts. However, standard XAS spectra inherently represent an average contribution from the entire coordination...

  2. Absorption spectroscopy with sub-angstrom beams: ELS in STEM

    Spence, John C. H.

    2006-03-01

    Electron-energy loss spectroscopy (EELS) performed using a modern transmission scanning electron microscope (STEM) now offers sub-nanometre spatial resolution and an energy resolution down to 200 meV or less, in favourable cases. The absorption spectra, which probe empty states, cover the soft x-ray region and may be obtained under conditions of well-defined momentum transfer (angle-resolved), providing a double projection onto crystallographic site and symmetry within the density of states. By combining the very high brightness of field-emission electron sources (brighter than a synchrotron) with the high cross-section of electron scattering, together with parallel detection (not possible with scanning x-ray absorption spectroscopy), a form of spectroscopy ideally suited to the study of nanostructures, interfacial states and defects in materials is obtained with uniquely high spatial resolution. We review the basic theory, the relationship of EELS to optical properties and the dielectric response function, the removal of multiple scattering artefacts and channelling effects. We consider applications in the light of recent developments in aberration corrector and electron monochromator design. Examples are cited of inner-shell spectra obtained from individual atoms within thin crystals, of the detection of interfacial electronic states in semiconductors, of inner-shell near edge structure mapped with sub-nanometre spatial resolution in glasses and of spectra obtained from individual carbon nanotubes, amongst many others.

  3. Hydrogen as a Modifier of the Structure and Electronic Properties of Platinum in Acidic Zeolite. LTL: A Combined Infrared and X-ray Absorption Spectroscopy Study.

    Koningsberger, D.C.; Vaarkamp, M.; Mojet, B.L.; Kappers, M.J.; Miller, J.T.

    1995-01-01

    The structure and electronic properties of platinum in WH-LTL after reduction at 300 'C and heating in helium to 500 or 690 'C were determined using X-ray absorption and infrared spectroscopy. After reduction at 300 'C, the platinum particles were metallic, consisted of 4 or 5 atoms, and were locate

  4. Non-linear and transient absorption spectroscopy of magnesium(II)-tetrabenzoporphyrin in solution

    Stiel, H.; Volkmer, A.; Rückmann, I.; Zeug, A.; Ehrenberg, B.; Röder, B.

    1998-10-01

    The excited state properties of magnesium(II)-tetrabenzoporphyrin (Mg-TBP) were studied by using intensity dependent transmission (non-linear absorption), ps-transient absorption and time resolved luminescence spectroscopy. It was found that there is a strong excited absorption in the region around 500 nm. Because there is no or little ground state absorption in this region the dye is suitable as an optical limiter.

  5. Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems.

    Berera, Rudi; van Grondelle, Rienk; Kennis, John T M

    2009-01-01

    The photophysical and photochemical reactions, after light absorption by a photosynthetic pigment-protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. The advent of ultrafast laser systems that produce pulses with femtosecond duration opened up a new area of research and enabled investigation of these photophysical and photochemical reactions in real time. Here, we provide a basic description of the ultrafast transient absorption technique, the laser and wavelength-conversion equipment, the transient absorption setup, and the collection of transient absorption data. Recent applications of ultrafast transient absorption spectroscopy on systems with increasing degree of complexity, from biomimetic light-harvesting systems to natural light-harvesting antennas, are presented. In particular, we will discuss, in this educational review, how a molecular understanding of the light-harvesting and photoprotective functions of carotenoids in photosynthesis is accomplished through the application of ultrafast transient absorption spectroscopy.

  6. Signaling-State Formation Mechanism of a BLUF Protein PapB from the Purple Bacterium Rhodopseudomonas palustris Studied by Femtosecond Time-Resolved Absorption Spectroscopy.

    Fujisawa, Tomotsumi; Takeuchi, Satoshi; Masuda, Shinji; Tahara, Tahei

    2014-12-26

    We studied the signaling-state formation of a BLUF (blue light using FAD) protein, PapB, from the purple bacterium Rhodopseudomonas palustris, using femtosecond time-resolved absorption spectroscopy. Upon photoexcitation of the dark state, FADH(•) (neutral flavin semiquinone FADH radical) was observed as the intermediate before the formation of the signaling state. The kinetic analysis based on singular value decomposition showed that FADH(•) mediates the signaling-state formation, showing that PapB is the second example of FADH(•)-mediated formation of the signaling state after Slr1694 (M. Gauden et al. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 10895-10900). The mechanism of the signaling-state formation is discussed on the basis of the comparison between femtosecond time-resolved absorption spectra of the dark state and those obtained by exciting the signaling state. FADH(•) was observed also with excitation of the signaling state, and surprisingly, the kinetics of FADH(•) was indistinguishable from the case of exciting the dark state. This result suggests that the hydrogen bond environment in the signaling state is realized before the formation of FADH(•) in the photocycle of PapB.

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

    Cai, Weiwei; Kaminski, Clemens F., E-mail: cfk23@cam.ac.uk [Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge CB2 3RA (United Kingdom)

    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.

  8. High resolution and high precision absorption spectroscopy using high finesse cavities: application to the study of molecules with atmospheric interest; Cavites de haute finesse pour la spectroscopie d'absorption haute sensibilite et haute precision: application a l'etude de molecules d'interet atmospherique

    Motto-Ros, V.

    2005-12-15

    High finesse cavities are used to measure very weak absorption features. Two different methodologies are investigated and applied to the study of molecules with atmospheric interest. First, Continuous Wave - Cavity Ring Down Spectroscopy (CW-CRDS) is used to study the atmospheric spectra of water vapour in the near infrared range. These measurements are performed for temperature and pressure of atmospheric relevance for DIAL applications (Differential Absorption Lidar). This study, financed by the European Space Agency (ESA), goes with the WALES mission (Water Vapour Lidar Experiment in Space). The experimental setup was conceived in order to control pressure, temperature and relative humidity conditions. A particular attention is done to characterize and describe the spectrometer. Then, measurements of red Oxygen B band are performed to demonstrate the huge performance of Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS). The desired optical feedback is obtained by light injection into the high finesse cavity through a glass plate placed inside the cavity and closed to the Brewster angle. We show a measurement dynamical range of 5 orders of magnitude (10{sup -5} to 10{sup -10} /cm) and a sensitivity of 10{sup -10} /cm/{radical} Hz. Also, sampling absorption spectra by the super linear cavity frequency comb allows very precise frequency measurements. This is demonstrated by the determination of Oxygen pressure shifts with an absolute accuracy of around 5 x 10{sup -5} cm{sup -1}/atm. To our knowledge, we provide the highest accuracy ever reported for this parameter. (author)

  9. Excited-state intramolecular proton transfer of 2-acetylindan-1,3-dione studied by ultrafast absorption and fluorescence spectroscopy

    Pramod Kumar Verma

    2016-03-01

    Full Text Available We employ transient absorption from the deep-UV to the visible region and fluorescence upconversion to investigate the photoinduced excited-state intramolecular proton-transfer dynamics in a biologically relevant drug molecule, 2-acetylindan-1,3-dione. The molecule is a ß-diketone which in the electronic ground state exists as exocyclic enol with an intramolecular H-bond. Upon electronic excitation at 300 nm, the first excited state of the exocyclic enol is initially populated, followed by ultrafast proton transfer (≈160 fs to form the vibrationally hot endocyclic enol. Subsequently, solvent-induced vibrational relaxation takes place (≈10 ps followed by decay (≈390 ps to the corresponding ground state.

  10. Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: Time-resolved EPR and transient absorption spectroscopy study

    Zhu, Guanglai; Wang, Yu; Fu, Haiying; Xu, Xinsheng; Cui, Zhifeng; Ji, Xuehan; Wu, Guozhong

    2015-02-01

    Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L-1 and TEA was 150 mmol L-1, indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L-1 and TEA was 2.2 mmol L-1, showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

  11. Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: time-resolved EPR and transient absorption spectroscopy study.

    Zhu, Guanglai; Wang, Yu; Fu, Haiying; Xu, Xinsheng; Cui, Zhifeng; Ji, Xuehan; Wu, Guozhong

    2015-02-25

    Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L(-1) and TEA was 150 mmol L(-1), indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L(-1) and TEA was 2.2 mmol L(-1), showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

  12. Local atomic structure investigation of AlFeCuCrMgx (0.5, 1, 1.7) high entropy alloys: X-ray absorption spectroscopy study

    Maulik, Ornov; Patra, N.; Bhattacharyya, D.; Jha, S. N.; Kumar, Vinod

    2017-02-01

    The present paper reports local atomic structure investigation of novel AlFeCuCrMgx (x=0.5, 1, 1.7) high entropy alloys (HEAs) produced by mechanical alloying using Fe, Cr and Cu K-edge X-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopy. XANES spectra measured at Fe and Cr K-edges resemble that of the respective pure metal foils, while the spectrum measured at Cu K-edge manifests the presence of some other phases in the as-milled alloys. The radial distribution functions (RDFs) obtained from Fourier transformation of EXAFS spectra support the formation of disordered BCC structure.

  13. Electron delocalization in cyanide-bridged coordination polymer electrodes for Li-ion batteries studied by soft x-ray absorption spectroscopy

    Asakura, Daisuke; Okubo, Masashi; Mizuno, Yoshifumi; Kudo, Tetsuichi; Zhou, Haoshen; Amemiya, Kenta; de Groot, Frank M. F.; Chen, Jeng-Lung; Wang, Wei-Cheng; Glans, Per-Anders; Chang, Chinglin; Guo, Jinghua; Honma, Itaru

    2011-01-01

    The electronic structure change during the reversible Li-ion storage reaction in a bimetallic MnFe-Prussian blue analogue (Li(x)K(0.14)Mn(1.43)[Fe(CN)(6)] center dot 6H(2)O) was investigated by soft x-ray absorption spectroscopy. The Mn L(2,3)-edgespectra revealed the unchanged Mn(2+) high-spin stat

  14. Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: X-ray absorption spectroscopy studies and biological applications.

    Silva, Telma F S; Martins, Luísa M D R S; Guedes da Silva, M Fátima C; Kuznetsov, Maxim L; Fernandes, Alexandra R; Silva, Ana; Pan, Chun-Jern; Lee, Jyh-Fu; Hwang, Bing-Joe; Pombeiro, Armando J L

    2014-04-01

    [CoCl(μ-Cl)(Hpz(Ph))3]2 (1) and [CoCl2(Hpz(Ph))4] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))3 and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible Co(II)→Co(III) oxidations and Co(II)→Co(I) reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). In situ X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co(III) site. Complex 2 showed low in vitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.

  15. Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

    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 .

  16. Arsenic speciation in solids using X-ray absorption spectroscopy

    Foster, Andrea L.; Kim, Chris S.

    2014-01-01

    Synchrotron-based X-ray absorption spectroscopy (XAS) is an in situ, minimally-destructive, element-specific, molecular-scale structural probe that has been employed to study the chemical forms (species) of arsenic (As) in solid and aqueous phases (including rocks, soils, sediment, synthetic compounds, and numerous types of biota including humans) for more than 20 years. Although several excellent reviews of As geochemistry and As speciation in the environment have been published previously (including recent contributions in this volume), the explosion of As-XAS studies over the past decade (especially studies employing microfocused X-ray beams) warrants this new review of the literature and of data analysis methods.

  17. Trace gas absorption spectroscopy using functionalized microring resonators.

    Stievater, Todd H; Pruessner, Marcel W; Park, Doewon; Rabinovich, William S; McGill, R Andrew; Kozak, Dmitry A; Furstenberg, Robert; Holmstrom, Scott A; Khurgin, Jacob B

    2014-02-15

    We detect trace gases at parts-per-billion levels using evanescent-field absorption spectroscopy in silicon nitride microring resonators coated with a functionalized sorbent polymer. An analysis of the microring resonance line shapes enables a measurement of the differential absorption spectra for a number of vapor-phase analytes. The spectra are obtained at the near-infrared overtone of OH-stretch resonance, which provides information about the toxicity of the analyte vapor.

  18. Study of apical oxygen atoms in a spin-ladder cuprate compound by X-ray absorption spectroscopy near the Cu K edge

    Hatterer, C.J.; Eustache, B.; Collin, L.; Beuran, C.F.; Partiot, C.; Germain, P.; Xu, X.Z.; Lagues, M. [CNRS, Paris (France). Surfaces et Supraconducteurs; Michalowicz, A. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France)]|[LURE, Universite Paris Sud, 91405, Orsay Cedex (France); Moscovici, J. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France); Deville Cavellin, C. [CNRS, Paris (France). Surfaces et Supraconducteurs]|[Laboratoire d`Electronique, Universite Paris XII Val-de-Marne, 61 av. du general de Gaulle, 94010, Creteil Cedex (France); Traverse, A. [LURE, Universite Paris Sud, 91405, Orsay Cedex (France)

    1997-04-01

    The structure of high-T{sub c} superconducting cuprate compounds is based on CuO{sub 2} planes alternating with blocks that behave as charge reservoirs. The apical oxygen atoms which belong to these reservoirs are suspected to play a role in the mechanism of superconductivity. It thus seems necessary to measure the amount of apical oxygen atoms in various compounds, as a function of the superconducting properties. Polarisation dependent X-ray absorption spectroscopy (XAS) measurements were performed near the Cu K-edge on three types of phases. We collected information about the neighbourhood of the copper atom in the cuprate planes and in the direction perpendicular to these planes. Two of these phases have well known structures: Bi2212 in which copper atoms are on a pyramidal site and infinite layer phase, a square planar cuprate without apical oxygen. We used the obtained results as reference data to study a new copper-rich phase related to the spin-ladder series. (orig.)

  19. Molecular shock response of explosives: electronic absorption spectroscopy

    Mcgrne, Shawn D [Los Alamos National Laboratory; Moore, David S [Los Alamos National Laboratory; Whitley, Von H [Los Alamos National Laboratory; Bolme, Cindy A [Los Alamos National Laboratory; Eakins, Daniel E [Los Alamos National Laboratory

    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.

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

    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.

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

    Zhao, W. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Chu, W.S.; Yang, F.F.; Yu, M.J.; Chen, D.L.; Guo, X.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhou, D.W.; Shi, N. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Niu, L.W.; Teng, M.K. [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230027 (China); Gong, W.M. [Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Benfatto, M. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy); Wu, Z.Y. [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, P.O. Box 13, Frascati 00044 (Italy)], E-mail: wuzy@ihep.ac.cn

    2007-09-21

    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.

  2. Self-calibration wavelength modulation spectroscopy for acetylene detection based on tunable diode laser absorption spectroscopy

    Huang, Qin-Bin; Xu, Xue-Mei; Li, Chen-Jing; Ding, Yi-Peng; Cao, Can; Yin, Lin-Zi; Ding, Jia-Feng

    2016-11-01

    The expressions of the second harmonic (2f) signal are derived on the basis of absorption spectral and lock-in theories. A parametric study indicates that the phase shift between the intensity and wavelength modulation makes a great contribution to the 2f signal. A self-calibration wavelength modulation spectroscopy (WMS) method based on tunable diode laser absorption spectroscopy (TDLAS) is applied, combining the advantages of ambient pressure, temperature suppression, and phase-shift influences elimination. Species concentration is retrieved simultaneously from selected 2f signal pairs of measured and reference WMS-2f spectra. The absorption line of acetylene (C2H2) at 1530.36 nm near-infrared is selected to detect C2H2 concentrations in the range of 0-400 ppmv. System sensitivity, detection precision and limit are markedly improved, demonstrating that the self-calibration method has better detecting performance than the conventional WMS. Project supported by the National Natural Science Foundation of China (Grant Nos. 61172047, 61502538, and 61501525).

  3. The decays of three top contributors to the reactor ve high-energy spectrum, 92Rb, 96gsY, and 142Cs, studied with total absorption spectroscopy

    Rasco, Bertis; MTAS Collaboration

    2016-09-01

    We report total absorption spectroscopy measurements of 92Rb, 96gsY, and 142Cs β decays, which are the most important contributors to the high energy ve spectral shape in nuclear reactors. The measurements were performed with the NaI(Tl) based Modular Total Absorption Spectrometer (MTAS). MTAS was constructed specifically to measure improved β-decay feeding patterns from neutron-rich nuclei, because it is difficult to measure β-decay feeding intensities with high energy precision γ-ray measurements due to the low efficiency of high precision detectors. Besides the impact to the high energy ve spectral shape in nuclear reactors, there are several other important applications of improved measurements of β-decay feeding patterns by total absorption spectroscopy; improve understanding of elemental abundances in the universe, help with stockpile stewardship, contribute to understanding of underlying nuclear structure, and improve measurements of decay heat. We will demonstrate some of the techniques for analyzing MTAS γ-decay data. This research was also sponsored by the Office of Nuclear Physics, U. S. Department of Energy under Contracts DE-AC05-00OR22725, DE-FG02-96ER40983, DE-FG02-96ER40978, and by the Polish National Science Center under Contract UMO-2013/08/T/ST2/00624.

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

    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.

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

    Serrano, A. [Instituto de Ceramica y Vidrio (ICV-CSIC), Cantoblanco, 28049 Madrid (Spain); Departamento de Fisica de Materiales, Universidad Complutense de Madrid, 28040 Madrid (Spain); Rodriguez de la Fuente, O. [Departamento de Fisica de Materiales, Universidad Complutense de Madrid, 28040 Madrid (Spain); Collado, V.; Rubio-Zuazo, J.; Castro, G. R. [SpLine, Spanish CRG Beamline at the ESRF, F-38043 Grenoble, Cedex 09, France and Instituto de Ciencia de Materiales de Madrid, (ICMM-CSIC), Cantoblanco, 28049 Madrid (Spain); Monton, C. [Department of Physics and Center for Advanced Nanoscience, University of California San Diego, La Jolla, California 92093 (United States); Garcia, M. A. [Instituto de Ceramica y Vidrio (ICV-CSIC), Cantoblanco, 28049 Madrid (Spain); IMDEA Nanociencia, Cantoblanco, 28049 Madrid (Spain)

    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.

  6. Absorption and emission spectroscopy in natural and synthetic corundum

    Spinolo, G.; Palanza, V.; Ledonne, A.; Paleari, A.

    2009-04-01

    sapphires absorption spectra. In conclusion, both for metamorphic, synthetic and magmatic sapphires we reached a quite complete interpretation of the spectroscopic data in terms of "non interacting impurity ions". Orange, purple and green sapphires absorption spectra may also be discussed in terms of such interpretative approach. References Fontana I, LeDonne A, Palanza V, Binetti S and Spinolo G (2008) Optical spectroscopy study of type 1 natural and synthetic sapphires. J. Phys:Condens.Matter 20:125228-125232

  7. Spectroscopy

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

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

    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)

  9. Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

    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…

  10. [Burner head with high sensitivity in atomic absorption spectroscopy].

    Feng, X; Yang, Y

    1998-12-01

    This paper presents a burner head with gas-sample separate entrance and double access, which is used for atomic absorption spectroscopy. According to comparison and detection, the device can improve sensitivity by a factor of 1 to 5. In the meantime it has properties of high stability and resistance to interference.

  11. Adsorption of isophorone and trimethyl-cyclohexanone on Pd(111): A combination of infrared reflection absorption spectroscopy and density functional theory studies

    Dostert, Karl-Heinz; O'Brien, Casey P.; Liu, Wei; Riedel, Wiebke; Savara, Aditya; Tkatchenko, Alexandre; Schauermann, Swetlana; Freund, Hans-Joachim

    2016-08-01

    Understanding the interaction of α,β-unsaturated carbonyl compounds with late transition metals is a key prerequisite for rational design of new catalysts with desired selectivity towards C = C or C = O bond hydrogenation. The interaction of the α,β-unsaturated ketone isophorone and the saturated ketone TMCH (3,3,5-trimethylcyclohexanone) with Pd(111) was investigated in this study as a prototypical system. Infrared reflection-absorption spectroscopy (IRAS) and density functional theory calculations including van der Waals interactions (DFT + vdWsurf) were combined to form detailed assignments of IR vibrational modes in the range from 3000 cm- 1 to 1000 cm- 1 in order to obtain information on the binding of isophorone and TMCH to Pd(111) as well as to study the effect of co-adsorbed hydrogen. IRAS measurements were performed with deuterium-labeled (d5-) isophorone, in addition to unlabeled isophorone and unlabeled TMCH. Experimentally observed IR absorption features and calculated vibrational frequencies indicate that isophorone and TMCH molecules in multilayers have a mostly unperturbed structure with random orientation. At sub-monolayer coverages, strong perturbation and preferred orientations of the adsorbates were found. At low coverage, isophorone interacts strongly with Pd(111) and adsorbs in a flat-lying geometry with the C = C and C = O bonds parallel, and a CH3 group perpendicular, to the surface. At intermediate sub-monolayer coverage, the C = C bond is strongly tilted, while the C = O bond remains flat-lying, which indicates a prominent perturbation of the conjugated π system. Pre-adsorbed hydrogen leads to significant changes in the adsorption geometry of isophorone, which suggests a weakening of its binding to Pd(111). At low coverage, the structure of the CH3 groups seems to be mostly unperturbed on the hydrogen pre-covered surface. With increasing coverage, a conservation of the in-plane geometry of the conjugated π system was observed in the

  12. Spin state transition in LaCoO3 studied using soft x-ray absorption spectroscopy and magnetic circular dichroism.

    Haverkort, M W; Hu, Z; Cezar, J C; Burnus, T; Hartmann, H; Reuther, M; Zobel, C; Lorenz, T; Tanaka, A; Brookes, N B; Hsieh, H H; Lin, H-J; Chen, C T; Tjeng, L H

    2006-10-27

    Using soft x-ray absorption spectroscopy and magnetic circular dichroism at the Co-L(2,3) edge, we reveal that the spin state transition in LaCoO3 can be well described by a low-spin ground state and a triply degenerate high-spin first excited state. From the temperature dependence of the spectral line shapes, we find that LaCoO3 at finite temperatures is an inhomogeneous mixed-spin state system. It is crucial that the magnetic circular dichroism signal in the paramagnetic state carries a large orbital momentum. This directly shows that the currently accepted low- or intermediate-spin picture is at variance. Parameters derived from these spectroscopies fully explain existing magnetic susceptibility, electron spin resonance, and inelastic neutron data.

  13. The extraction of gold nanoparticles from oat and wheat biomasses using sodium citrate and cetyltrimethylammonium bromide, studied by x-ray absorption spectroscopy, high-resolution transmission electron microscopy, and UV-visible spectroscopy

    Armendariz, Veronica; Parsons, Jason G.; Lopez, Martha L.; Peralta-Videa, Jose R.; Jose-Yacaman, Miguel; Gardea-Torresdey, Jorge L.

    2009-03-01

    Gold (Au) nanoparticles can be produced through the interaction of Au(III) ions with oat and wheat biomasses. This paper describes a procedure to recover gold nanoparticles from oat and wheat biomasses using cetyltrimethylammonium bromide or sodium citrate. Extracts were analyzed using UV-visible spectroscopy, high-resolution transmission electron microscopy (HRTEM), and x-ray absorption spectroscopy. The HRTEM data demonstrated that smaller nanoparticles are extracted first, followed by larger nanoparticles. In the fourth extraction, coating of chelating agents is visible on the extracted nanoparticles.

  14. Polarization-enhanced absorption spectroscopy for laser stabilization.

    Kunz, Paul D; Heavner, Thomas P; Jefferts, Steven R

    2013-11-20

    We demonstrate a variation of pump-probe spectroscopy that is particularly useful for laser frequency stabilization. The polarization-enhanced absorption spectroscopy (POLEAS) signal provides a significant improvement in signal-to-noise ratio over saturated absorption spectroscopy (SAS) for the important and commonly used atomic cycling transitions. The improvements can directly increase the short-term stability of a laser frequency lock, given sufficient servo loop bandwidth. The long-term stability of the POLEAS method, which is limited by environmental sensitivities, is comparable to that of SAS. The POLEAS signal is automatically Doppler-free, without requiring a separate Doppler subtraction beam, and lends itself to straightforward compact packaging. Finally, by increasing the amplitude of the desired (cycling) peak, while reducing the amplitude of all other peaks in the manifold, the POLEAS method eases the implementation of laser auto-locking schemes.

  15. Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection-absorption spectroscopy and temperature programmed desorption study.

    Dostert, Karl-Heinz; O'Brien, Casey P; Mirabella, Francesca; Ivars-Barceló, Francisco; Schauermann, Swetlana

    2016-05-18

    Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C[double bond, length as m-dash]C vs. C[double bond, length as m-dash]O bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection-absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the C[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported.

  16. Mechanism of Selenite Removal by a Mixed Adsorbent Based on Fe–Mn Hydrous Oxides Studied Using X-ray Absorption Spectroscopy

    Chubar, Natalia

    2014-11-18

    © 2014 American Chemical Society. Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3 2- trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

  17. Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy

    Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-10-01

    The catalytic hydrogenation of ethylene promoted by a Pt(111) single crystal was studied by using a ultrahigh-vacuum surface-science instrument equipped with a so-called high-pressure cell. Kinetic data were acquired continuously during the catalytic conversion of atmospheric-pressure mixtures of ethylene and hydrogen by using mass spectrometry while simultaneously characterizing the surface species in operando mode by reflection-absorption infrared spectroscopy (RAIRS). Many observations reported in previous studies of this system were corroborated, including the presence of adsorbed alkylidyne intermediates during the reaction and the zero-order dependence of the rate of hydrogenation on the pressure of ethylene. In addition, the high quality of the kinetic data, which could be recorded continuously versus time and processed to calculate time-dependent turnover frequencies (TOFs), afforded a more detailed analysis of the mechanism. Specifically, deuterium labeling could be used to estimate the extent of isotope scrambling reached with mixed-isotope-substituted reactants (C2H4 + D2 and C2D4 + H2). Perhaps the most important new observation from this work is that, although extensive H-D exchange takes place on ethylene before being fully converted to ethane, the average stoichiometry of the final product retains the expected stoichiometry of the gas mixture, that is, four regular hydrogen atoms and two deuteriums per ethane molecule in the case of the experiments with C2H4 + D2. This means that no hydrogen atoms are removed from the surface via their inter-recombination to produce X2 (X = H or D). It is concluded that, under catalytic conditions, hydrogen surface recombination is much slower than ethylene hydrogenation and H-D exchange.

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

    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.

  19. An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

    Carta, D; Marras, C; Loche, D; Mountjoy, G; Ahmed, S I; Corrias, A

    2013-02-07

    The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

  20. Studies on best dose of X-ray for Hep-2 cells by using FTIR, UV-vis absorption spectroscopy and flow cytometry.

    Liu, Renming; Tang, Weiyue; Kang, Yipu; Si, Minzhen

    2009-08-15

    We report here the use of Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-vis) absorption spectroscopy, and flow cytometry (FCM) to analysis the best dose of X-ray for human laryngeal squamous cell carcinoma cell lines (Hep-2). Our analysis indicates specific FTIR and UV-vis spectral differences between X-irradiated and normal Hep-2 cells. In addition, striking spectral differences are seen in FTIR spectra in the ratios at 2925/2958 and 1654/1542 cm(-1). These two ratios of the X-irradiated cells for 8 Gy dose group with value of 1.07+/-0.025 and 1.184+/-0.013, respectively, were more notable (mean+/-S.D., n=5, PUV-vis absorption spectra analysis shows X-ray irradiation disturbed the metabolism of phenylalanine and tyrosine intracellular, maybe, which was caused by cell cycle arrest. Spectroscopy analysis suggests 8 Gy is a better dose of X-ray for lowering the canceration degree of Hep-2 cells. Moreover, FCM analysis shows the apoptosis of X-irradiated cells depended on the radiation dose to some extent, but it was not linear. The total apoptosis ratio with value of (20.793+/-1.133)% (P<0.01, n=5) for the 12 Gy dose group was the maximum, however, the maximum apoptosis ratio per Gray (total apoptosis ratio/radiation dose) was the cells of the 2 Gy dose group with value of (4.887+/-0.211)% (P<0.05, n=5). Our data suggest that Hep-2 cells are given 2 Gy radiation of X-ray once a time, 8 Gy per week (accumulatively), the effect for lowering the canceration degree and restraining the proliferation of Hep-2 cells will be better.

  1. Antimony(III) complexing with O-bearing organic ligands in aqueous solution: An X-ray absorption fine structure spectroscopy and solubility study

    Tella, Marie; Pokrovski, Gleb S.

    2009-01-01

    The stability and structure of aqueous complexes formed by trivalent antimony (Sb III) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of Sb III hydroxide species, Sb(OH)3-nn+,Sb(OH)30andSb(OH)4-, at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, Sb III forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 cycle. Stability constants for these species, generated from Sb 2O 3 (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of complexed Sb for typical natural DOC concentrations is in agreement with that estimated from dialysis experiments performed with commercial humic acid in our work and those available in the literature for a range of standardized IHSS humic acids. Our results imply that a significant part of Sb is likely to be bound with humic acids via

  2. Study of atomic clusters in neutron irradiated reactor pressure vessel surveillance samples by extended X-ray absorption fine structure spectroscopy

    Cammelli, S. [LWV, NES, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Fachbereich C - Physik, Bergische Universitaet Wuppertal, Gauss-Str. 20, 42097 Wuppertal (Germany)], E-mail: Sebastiano.cammelli@psi.ch; Degueldre, C.; Kuri, G.; Bertsch, J. [LWV, NES, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Luetzenkirchen-Hecht, D.; Frahm, R. [Fachbereich C - Physik, Bergische Universitaet Wuppertal, Gauss-Str. 20, 42097 Wuppertal (Germany)

    2009-03-31

    Copper and nickel impurities in nuclear reactor pressure vessel (RPV) steel can form nano-clusters, which have a strong impact on the ductile-brittle transition temperature of the material. Thus, for control purposes and simulation of long irradiation times, surveillance samples are submitted to enhanced neutron irradiation. In this work, surveillance samples from a Swiss nuclear power plant were investigated by extended X-ray absorption fine structure spectroscopy (EXAFS). The density of Cu and Ni atoms determined in the first and second shells around the absorber is affected by the irradiation and temperature. The comparison of the EXAFS data at Cu and Ni K-edges shows that these elements reside in arrangements similar to bcc Fe. However, the EXAFS analysis reveals local irradiation damage in the form of vacancy fractions, which can be determined with a precision of {approx}5%. There are indications that the formation of Cu and Ni clusters differs significantly.

  3. X-ray absorption near the edge structure and x-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

    Zhang Hui; Liu Ying-Shu; Wang Bao-Yi; Wei Long; Kui Re-Xi; Qian Hai-Jie

    2009-01-01

    This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by x-ray absorption near edge structure spectra and x-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t2g and eg levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.

  4. X-ray absorption spectroscopy study of parent misfit-layered cobalt oxide [Sr2O2]qCoO2

    Chou, Ta-Lei; Chan, Ting-Shan; Chen, Jin-Ming; Yamauchi, Hisao; Karppinen, Maarit

    2013-06-01

    Here we present a comprehensive X-ray absorption spectroscopy study carried out at Co-L2,3, Co-K, O-K and Sr-K edges for the parent misfit-layered cobalt oxide phase [Sr2O2]0.52CoO2; comparison is made to another misfit-layered oxide [CoCa2O3]0.62CoO2 and the perovskite oxide LaCoO3. A high-quality sample of [Sr2O2]0.52CoO2 was obtained through ultra-high-pressure synthesis using Sr3Co2O6 and Sr(OH)2•8H2O as starting materials. Different dosages of KClO3 were mixed with the raw materials as an oxygen source and tested, but it was found that the window for the redox control of [Sr2O2]0.52CoO2 is rather narrow. From Co-K and Co-L2,3 spectra a mixed III/IV valence state is revealed for cobalt in [Sr2O2]0.52CoO2, but the average valence value is a little lower than in [CoCa2O3]0.62CoO2. Then, Sr-K spectrum indicates that the [Sr2O2] double-layer block in [Sr2O2]0.52CoO2 clearly deviates from the cubic SrO rock-salt structure, suggesting a more complicated coordination environment for strontium. This together with a somewhat low Co-valence value and the fact that the phase formation of [Sr2O2]0.52CoO2 required the presence of Sr(OH)2•8H2O in the high-pressure synthesis suggest that the [Sr2O2] block contains OH groups, i.e. [Sr2(O,OH)2]0.52CoO2.

  5. Combined time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure spectroscopy study on the complexation of trivalent actinides with chloride at T = 25-200 °C.

    Skerencak-Frech, Andrej; Fröhlich, Daniel R; Rothe, Jörg; Dardenne, Kathy; Panak, Petra J

    2014-01-21

    The complexation of trivalent actinides (An(III)) with chloride is studied in the temperature range from 25 to 200 °C by spectroscopic methods. Time-resolved laser fluorescence spectroscopy (TRLFS) is applied to determine the thermodynamic data of Cm(III)-Cl(-) complexes, while extended X-ray absorption fine structure spectroscopy (EXAFS) is used to determine the structural data of the respective Am(III) complexes. The experiments are performed in a custom-built high-temperature cell which is modified for the respective spectroscopic technique. The TRLFS results show that at 25 °C the speciation is dominated mainly by the Cm(3+) aquo ion. Only a minor fraction of the CmCl(2+) complex is present in solution. As the temperature increases, the fraction of this species decreases further. Simultaneously, the fraction of the CmCl2(+) complex increases strongly with the temperature. Also, the CmCl3 complex is formed to a minor extent at T > 160 °C. The conditional stability constant log β'2 is determined as a function of the temperature and extrapolated to zero ionic strength with the specific ion interaction theory approach. The log β°2(T) values increase by more than 3 orders of magnitude in the studied temperature range. The temperature dependency of log β°2 is fitted by the extended van't Hoff equation to determine ΔrH°m, ΔrS°m, and ΔrC°p,m. The EXAFS results support these findings. The results confirm the absence of americium(III) chloride complexes at T = 25 and 90 °C ([Am(III)] = 10(-3) m, [Cl(-)] = 3.0 m), and the spectra are described by 9-10 oxygen atoms at a distance of 2.44-2.48 Å. At T = 200 °C two chloride ligands are present in the inner coordination sphere of Am(III) at a distance of 2.78 Å.

  6. Studies on best dose of X-ray for Hep-2 cells by using FTIR, UV-vis absorption spectroscopy and flow cytometry

    Liu, Renming; Tang, Weiyue; Kang, Yipu; Si, Minzhen

    2009-08-01

    We report here the use of Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-vis) absorption spectroscopy, and flow cytometry (FCM) to analysis the best dose of X-ray for human laryngeal squamous cell carcinoma cell lines (Hep-2). Our analysis indicates specific FTIR and UV-vis spectral differences between X-irradiated and normal Hep-2 cells. In addition, striking spectral differences are seen in FTIR spectra in the ratios at 2925/2958 and 1654/1542 cm -1. These two ratios of the X-irradiated cells for 8 Gy dose group with value of 1.07 ± 0.025 and 1.184 ± 0.013, respectively, were more notable (mean ± S.D., n = 5, P phenylalanine and tyrosine intracellular, maybe, which was caused by cell cycle arrest. Spectroscopy analysis suggests 8 Gy is a better dose of X-ray for lowering the canceration degree of Hep-2 cells. Moreover, FCM analysis shows the apoptosis of X-irradiated cells depended on the radiation dose to some extent, but it was not linear. The total apoptosis ratio with value of (20.793 ± 1.133)% ( P < 0.01, n = 5) for the 12 Gy dose group was the maximum, however, the maximum apoptosis ratio per Gray (total apoptosis ratio/radiation dose) was the cells of the 2 Gy dose group with value of (4.887 ± 0.211)% ( P < 0.05, n = 5). Our data suggest that Hep-2 cells are given 2 Gy radiation of X-ray once a time, 8 Gy per week (accumulatively), the effect for lowering the canceration degree and restraining the proliferation of Hep-2 cells will be better.

  7. CO sub 2 absorption of perovskites as seen by positron lifetime spectroscopy

    Suevegh, K; Juhasz, G; Homonnay, Z; Vertes, A

    2000-01-01

    The CO sub 2 absorption of several ABO sub 3 type perovskites was studied by positron lifetime spectroscopy. The longer positron lifetime was associated with positrons trapped by A site vacancies. The evaluated positron lifetime data indicated the relative stability of the crystal structure of Sr(Co sub 0 sub . sub 5 Fe sub 0 sub . sub 5)O sub 3 sub - subdelta against Ca doping at low Ca concentrations. Oxygen desorption and CO sub 2 absorption/desorption could also be followed by positron lifetime spectroscopy. It was shown that the concentration of oxygen vacancies has a large effect on positron lifetime data through the electron density of A site vacancies.

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

    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.

  9. Structure of reactively sputter deposited tin-nitride thin films: A combined X-ray photoelectron spectroscopy, in situ X-ray reflectivity and X-ray absorption spectroscopy study

    Luetzenkirchen-Hecht, Dirk [Fachbereich C-Physik, Bergische Universitaet Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany)]. E-mail: dirklh@uni-wuppertal.de; Frahm, Ronald [Fachbereich C-Physik, Bergische Universitaet Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany)

    2005-12-22

    Amorphous tin-nitride thin films were prepared by reactive sputter deposition on smooth float glass substrates in a vacuum chamber with an integrated small magnetron source. The films were investigated using in situ reflection mode X-ray absorption spectroscopy and ex situ X-ray photoelectron spectroscopy (XPS). Both the X-ray absorption near edge structure (XANES) and the extended X-ray absorption fine structure (EXAFS) were analysed, yielding bond distances, coordination numbers and Debye-Waller factors. XPS yields the chemical composition and the binding state of the constituents of the films, specular X-ray reflectivity allows the determination of the sample density and of the roughness and its changes with film thickness. The results were compared to those of crystalline Sn{sub 3}N{sub 4}, indicating that the electronic and atomic structure of the amorphous films determined by EXAFS data analysis are very similar to the stoichiometric reference compound. Two different Sn-N interactions with about 2.09 and 2.19 A bond distance and 4 and 6 nearest neighbours, respectively, are present. These bond distances are slightly relaxed compared to the crystalline reference material, which is consistent with the sample density, which is reduced by about 8% in comparison to Sn{sub 3}N{sub 4}. XPS as well as XANES revealed a Sn valence of about 4+ and the presence of nitric bonds, while XPS also suggests that the nitride is slightly decomposed under X-ray irradiation in ultra-high vacuum.

  10. Diagnostic potential of cosmic-neutrino absorption spectroscopy

    Barenboim, Gabriela; /Valencia U.; 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.

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

    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.

  12. Quantitative analysis of immobilized metalloenzymes by atomic absorption spectroscopy.

    Opwis, Klaus; Knittel, Dierk; Schollmeyer, Eckhard

    2004-12-01

    A new, sensitive assay for the quantitative determination of immobilized metal containing enzymes has been developed using atomic absorption spectroscopy (AAS). In contrast with conventionally used indirect methods the described quantitative AAS assay for metalloenzymes allows more exact analyses, because the carrier material with the enzyme is investigated directly. As an example, the validity and reliability of the method was examined by fixing the iron-containing enzyme catalase on cotton fabrics using different immobilization techniques. Sample preparation was carried out by dissolving the loaded fabrics in sulfuric acid before oxidising the residues with hydrogen peroxide. The iron concentrations were determined by flame atomic absorption spectrometry after calibration of the spectrometer with solutions of the free enzyme at different concentrations.

  13. Optical Absorption Spectroscopy for Gas Analysis in Biomass Gasification

    Grosch, Helge

    the concentration of the mentioned compounds. However, continuous measurements of different species directly in the gas (in-situ) and at the same time are scarce. In this work, the basis of optical in-situ analysis with ultraviolet and infrared spectroscopy was build to determine the concentration of the most...... important gas species of the low-temperature circulating fluidized bed gasifier. At first, a special gas cell,the hot gas flow cell (HGC), was build up and veried. In this custom-made gas cell, the optical properties, the so-called absorption cross-sections, of the most important sulfur and aromatic...

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

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

    2016-01-05

    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.

  15. Shape effects along the Z=82 line: study of the $\\beta$- decay of $^{188,190,192}$Pb using total absorption spectroscopy

    Caballero ontanaya, L; Garcia borge, M J; Malbrunot, S

    2002-01-01

    This proposal is aimed at the study of the $\\beta$- decay of the neutron-deficient $^{188,190,192}$Pb nuclei. The main motivation of the proposed experiment is to determine the Gamow-Teller strength distribution in the daughter nuclei using the Total Absorption Spectrometer "Lucrecia". Recent theoretical results show that from this measurement the shapes of the ground states of the decaying Pb nuclei can be inferred. This study offers an independent way to study the phenomenon of shape co-existence in a region of particular interest.

  16. Methanogenic activity tests by Infrared Tunable Diode Laser Absorption Spectroscopy.

    Martinez-Cruz, Karla; Sepulveda-Jauregui, Armando; Escobar-Orozco, Nayeli; Thalasso, Frederic

    2012-10-01

    Methanogenic activity (MA) tests are commonly carried out to estimate the capability of anaerobic biomass to treat effluents, to evaluate anaerobic activity in bioreactors or natural ecosystems, or to quantify inhibitory effects on methanogenic activity. These activity tests are usually based on the measurement of the volume of biogas produced by volumetric, pressure increase or gas chromatography (GC) methods. In this study, we present an alternative method for non-invasive measurement of methane produced during activity tests in closed vials, based on Infrared Tunable Diode Laser Absorption Spectroscopy (MA-TDLAS). This new method was tested during model acetoclastic and hydrogenotrophic methanogenic activity tests and was compared to a more traditional method based on gas chromatography. From the results obtained, the CH(4) detection limit of the method was estimated to 60 ppm and the minimum measurable methane production rate was estimated to 1.09(.)10(-3) mg l(-1) h(-1), which is below CH(4) production rate usually reported in both anaerobic reactors and natural ecosystems. Additionally to sensitivity, the method has several potential interests compared to more traditional methods among which short measurements time allowing the measurement of a large number of MA test vials, non-invasive measurements avoiding leakage or external interferences and similar cost to GC based methods. It is concluded that MA-TDLAS is a promising method that could be of interest not only in the field of anaerobic digestion but also, in the field of environmental ecology where CH(4) production rates are usually very low.

  17. Precision atomic beam density characterization by diode laser absorption spectroscopy

    Oxley, Paul; Wihbey, Joseph

    2016-09-01

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10-5 are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 104 atoms cm-3. The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

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

    Leen, J. Brian, E-mail: b.leen@lgrinc.com; O’Keefe, Anthony [Los Gatos Research, 67 E. Evelyn Avenue, Suite 3, Mountain View, California 94041 (United States)

    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.

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

    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.

  20. Defects in a mixed-habit Yakutian diamond: Studies by optical and cathodoluminescence microscopy, infrared absorption, Raman scattering and photoluminescence spectroscopy

    Lang, A. R.; Bulanova, G. P.; Fisher, D.; Furkert, S.; Sarua, A.

    2007-12-01

    Widespread occurrences in the crystallisation history of natural diamonds are epochs of mixed-habit growth in which normal {1 1 1}-faceted growth is accompanied by non-faceted growth on curved surfaces of mean orientation ˜{1 0 0}, termed 'cuboid'. This paper analyses mixed-habit-related phenomena in a near-central, (1 1 0)-polished slice of an octahedron from the Mir pipe, previously studied principally by SIMS probes analysing N impurity content and C and N isotope composition. In the present work, newly studied features include dislocation content, fine structure in cathodoluminescence (CL) patterns, refined IR absorption data, Raman and photoluminescence (PL) microspectroscopy and microscopy of internal non-diamond bodies. Topographic imaging and spectroscopic techniques traced the specimen's morphological evolution from a cubo-octahedral core containing complex relative development of {1 1 1} and cuboid sectors, both populated by graphite crystallites, diameters up to ˜5 μm, lying on all diamond host {1 1 1}. Coherently overgrowing the core was a zone of widely but smoothly varying relative development of {1 1 1} and cuboid sectors, both on birefringence evidence dislocation-free, emitting strongly from cuboid sectors the PL spectra associated with Ni-N-vacancy complexes. An enclosing octahedral shell of solely {1 1 1} lamellae terminated mixed-habit growth. High-resolution FTIR absorption measurements of I( B'), the integrated absorption due to {1 0 0}-platelet defects, showed from its absence or weakness that total or substantial platelet degradation had taken place in the mixed-habit zones, indicating that these had undergone conditions close to the diamond-graphite phase boundary in their history.

  1. Optical absorption and scattering spectroscopies of single nano-objects.

    Crut, Aurélien; Maioli, Paolo; Del Fatti, Natalia; Vallée, Fabrice

    2014-06-07

    Developments of optical detection and spectroscopy methods for single nano-objects are key advances for applications and fundamental understanding of the novel properties exhibited by nanosize systems. These methods are reviewed, focusing on far-field optical approaches based on light absorption and elastic scattering. The principles of the main linear and nonlinear methods are described and experimental results are illustrated in the case of metal nanoparticles, stressing the key role played by the object environment, such as the presence of a substrate, bound surface molecules or other nano-objects. Special attention is devoted to quantitative methods and correlation of the measured optical spectra of a nano-object with its morphology, characterized either optically or by electron microscopy, as this permits precise comparison with theoretical models. Application of these methods to optical detection and spectroscopy for single semiconductor nanowires and carbon nanotubes is also presented. Extension to ultrafast nonlinear extinction or scattering spectroscopies of single nano-objects is finally discussed in the context of investigation of their nonlinear optical response and their electronic, acoustic and thermal properties.

  2. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    Fischer, D.A. [National Institute of Standards and Technology, Gaithersburg, MD (United States); Mitchell, G.E.; Dekoven, B.M. [Dow Chemical Co., Midland, MI (United States); Yeh, A.T.; Gland, J.L. [Michigan Univ., Ann Arbor, MI (United States); Moodenbaugh, A.R. [Brookhaven National Lab., Upton, NY (United States)

    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.

  3. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    Fischer, D.A. (National Institute of Standards and Technology, Gaithersburg, MD (United States)); Mitchell, G.E.; Dekoven, B.M. (Dow Chemical Co., Midland, MI (United States)); Yeh, A.T.; Gland, J.L. (Michigan Univ., Ann Arbor, MI (United States)); Moodenbaugh, A.R. (Brookhaven National Lab., Upton, NY (United States))

    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.

  4. The influence of surface passivation on electronic energy relaxation dynamics of CdSe and CdSe/CdS nanocrystals studied using visible and near infrared transient absorption spectroscopy.

    Yi, Chongyue; Knappenberger, Kenneth L

    2015-03-19

    Charge carrier relaxation dynamics of electronically excited CdSe and CdSe/CdS core/shell nanocrystals (NCs) were studied using femtosecond time-resolved transient absorption spectroscopy, employing both visible and near-infrared (NIR) probe laser pulses. Following 400 nm excitation, the combination of visible and NIR laser probe pulses were used to determine the influence of surface passivation on electronic relaxation dynamics for nanocrystals overcoated with either organic ligands or inorganic semiconductors. In particular, low-energy NIR photons were used to isolate transient absorption signals due to either electron and hole intraband transitions. Four relaxation components were detected for CdSe NCs passivated by organic molecules: (1) picosecond hole relaxation; (2) electron deep trapping; (3) electron surface trapping; and (4) exciton radiative recombination. Based on TA data collected over a broad energy range, electron deep trapping at Se(2-) sites was suppressed for CdSe NCs passivated by inorganic (CdS) semiconducting materials. By comparing the time-dependent transient absorption data of a series of CdSe/CdS NCs with different shell thicknesses, evidence for the transition from Type-I to quasi Type-II NCs was obtained. These data illustrate the sensitivity of femtosecond time-resolved transient absorption measurements carried out over visible and near infrared probe energies for determining the influence of nanocrystal structure on electronic relaxation dynamics.

  5. Absorption of copper(II) by creosote bush (Larrea tridentata): use of atomic and x-ray absorption spectroscopy.

    Gardea-Torresdey, J L; Arteaga, S; Tiemann, K J; Chianelli, R; Pingitore, N; Mackay, W

    2001-11-01

    Larrea tridentata (creosote bush), a common North American native desert shrub, exhibits the ability to take up copper(II) ions rapidly from solution. Following hydroponic studies, U.S. Environmental Protection Agency method 200.3 was used to digest the plant samples, and flame atomic absorption spectroscopy (FAAS) was used to determine the amount of copper taken up in different parts of the plant. The amount of copper(II) found within the roots, stems, and leaves was 13.8, 1.1, and 0.6 mg/g, respectively, after the creosote bush was exposed to a 63.5-ppm copper(II) solution for 48 h. When the plant was exposed to a 635-ppm copper(II) solution, the roots, stems, and leaves contained 35.0, 10.5, and 3.8 mg/g, respectively. In addition to FAAS analysis, x-ray microfluorescence (XRMF) analysis of the plant samples provided further confirmation of copper absorption by the various plant parts. X-ray absorption spectroscopy (XAS) elucidated the oxidation state of the copper absorbed by the plants. The copper(II) absorbed from solution remained as copper(II) bound to oxygen-containing ligands within the plant samples. The results of this study indicate that creosote bush may provide a useful and novel method of removing copper(II) from contaminated soils in an environmentally friendly manner.

  6. High Resolution Absorption Spectroscopy using Externally Dispersed Interferometry

    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.

  7. Terahertz absorption spectroscopy of protein-containing reverse micellar solution

    Murakami, H.; Toyota, Y.; Nishi, T.; Nashima, S.

    2012-01-01

    Terahertz time-domain spectroscopy has been carried out for AOT/isooctane reverse micellar solution with myoglobin at the water-to-surfactant molar ratios ( w0) of 0.2 and 4.4. The amplitude of the absorption spectrum increases with increasing the protein concentration at w0 = 0.2, whereas it decreases at w0 = 4.4. The molar extinction coefficients of the protein-filled reverse micelle, and the constituents, i.e., myoglobin, water, and AOT, have been derived by use of the structural parameters of the micellar solution. The experimental results are interpreted in terms of hydration onto the protein and surfactant in the reverse micelle.

  8. Simultaneous Surface Plasmon Resonance and X-ray Absorption Spectroscopy

    Serrano, A; Collado, V; Rubio-Zuazo, J; Monton, C; Castro, G; García, M A

    2012-01-01

    We present here an experimental set-up to perform simultaneously measurements of surface plasmon resonance (SPR) and X-ray absorption spectroscopy (XAS) in 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 detect the changes in the electronic configuration of thin films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be carried out. The relative variations in the SPR and XAS spectra that can be detected with this set-up ranges from 10-3 to 10-5, depending on the particular experiment.

  9. La Saturated Absorption Spectroscopy for Applications in Quantum Information

    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.

  10. Antimony quantification in Leishmania by electrothermal atomic absorption spectroscopy.

    Roberts, W L; Rainey, P M

    1993-05-15

    Tri- and pentavalent antimony were quantified in Leishmania mexicana pifanoi amastigotes and promastigotes by atomic absorption spectroscopy with electrothermal atomization. Leishmania grown in axenic culture were treated with either potassium antimony tartrate [Sb(III)] or sodium stibogluconate [Sb(V)]. The parasites were collected, digested with nitric acid, and subjected to atomic absorption spectroscopy. The method was linear from 0 to 7 ng of antimony. The interassay coefficients of variation were 9.6 and 5.7% (N = 5) for 0.52 and 3.7-ng samples of leishmanial antimony, respectively. The limit of detection was 95 pg of antimony. The assay was used to characterize Sb(III) and Sb(V) influx and efflux kinetics. Influx rates were determined at antimony concentrations that produced a 50% inhibition of growth (IC50). The influx rates of Sb(V) into amastigotes and promastigotes were 4.8 and 12 pg/million cells/h, respectively, at 200 micrograms antimony/ml. The influx rate of Sb(III) into amastigotes was 41 pg/million cells/h at 20 micrograms antimony/ml. Influx of Sb(III) into promastigotes at 1 microgram antimony/ml was rapid and reached a plateau of 175 pg/million cells in 2 h. Efflux of Sb(III) and Sb(V) from amastigotes and promastigotes exhibited biphasic kinetics. The initial (alpha) half-life of Sb(V) efflux was less than 4 min and that of Sb(III) was 1-2 h. The apparent terminal (beta) half-lives ranged from 7 to 14 h.

  11. Determining Concentrations and Temperatures in Semiconductor Manufacturing Plasmas via Submillimeter Absorption Spectroscopy

    Helal, Yaser H.; Neese, Christopher F.; De Lucia, Frank C.; Ewing, Paul R.; Agarwal, Ankur; Craver, Barry; Stout, Phillip J.; Armacost, Michael D.

    2016-06-01

    Plasmas used in the manufacturing processes of semiconductors are similar in pressure and temperature to plasmas used in studying the spectroscopy of astrophysical species. Likewise, the developed technology in submillimeter absorption spectroscopy can be used for the study of industrial plasmas and for monitoring manufacturing processes. An advantage of submillimeter absorption spectroscopy is that it can be used to determine absolute concentrations and temperatures of plasma species without the need for intrusive probes. A continuous wave, 500 - 750 GHz absorption spectrometer was developed for the purpose of being used as a remote sensor of gas and plasma species. An important part of this work was the optical design to match the geometry of existing plasma reactors in the manufacturing industry. A software fitting routine was developed to simultaneously fit for the background and absorption signal, solving for concentration, rotational temperature, and translational temperature. Examples of measurements made on inductively coupled plasmas will be demonstrated. We would like to thank the Texas Analog Center of Excellence/Semiconductor Research Corporation (TxACE/SRC) and Applied Materials for their support of this work.

  12. Interactions of hypericin with a model mutagen - Acridine orange analyzed by light absorption and fluorescence spectroscopy

    Pietrzak, Monika; Szabelski, Mariusz; Kasparek, Adam; Wieczorek, Zbigniew

    2017-02-01

    The present study was designed to estimate the ability of hypericin to interact with a model mutagen - acridine orange. The hetero-association of hypericin and acridine orange was investigated with absorption and fluorescence spectroscopy methods in aqueous solution of DMSO. The data indicate that hypericin forms complexes with acridine orange and that the association constants are relatively high and depend on DMSO concentration. The absorption spectra of the hypericin - acridine orange complexes were examined as well. Owing to its ability to interact with flat aromatic compounds, hypericin may potentially be used as an interceptor molecule.

  13. Study of the electronic properties of Zn{sub 0.8–4x}Ho{sub x}O{sub y} (0.05 ≤ x ≤ 0.09) by X-ray absorption and photoemission spectroscopy

    Ekicibil, A. [Physic Department, University of Cukurova, 01330 Adana (Turkey); Ozkendir, O.M. [Tarsus Technology Faculty, Mersin University, 33400 Tarsus (Turkey); Farha, A.H. [Department of Electrical and Computer Engineering, Old Dominion University, Norfolk, VA 23529 (United States); Department of Physics, Faculty of Science, Ain Shams University, Cairo 11566 (Egypt); Ufuktepe, Y., E-mail: ufuk@cu.edu.tr [Physic Department, University of Cukurova, 01330 Adana (Turkey)

    2015-07-15

    Highlights: • The electronic structure of Ho doped ZnO was investigated by XANES and XPS. • The electronic structure was directly influenced by the Ho concentration in the ZnO. • The crystal structure showed little/no correlation to the substitution of Ho. • The substitution of Ho causes a weaker antiferromagnetic interaction. • The blue shift in band gap is observed and discussed. - Abstract: The electronic structure of Zn{sub 0.8–4x}Ho{sub x}O{sub y} (0.05 ≤ x ≤ 0.09) was investigated using X-ray absorption near edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). Samples were prepared by the solid state reaction method. Using X-ray absorption spectroscopy, the investigation of M{sub 4,5} absorption edge of Ho revealed that the electronic structure was directly influenced by the Ho concentration in the Zn{sub 0.8–4x}Ho{sub x}O{sub y} sample whereas the crystal structure properties showed little/no correlation to the substitution of Ho. The electronic structure differs substantially from those of the reference ZnO. The O K-edge spectra suggest that the combination of the Ho with ZnO enhances the effective charge of the O ions. A systematic study on the composition from lower to higher value of Ho dopant showed the blue shift in band gaps and is discussed in the view of the electronic structure of the Zn{sub 0.8–4x}Ho{sub x}O{sub y} samples. The inverse susceptibility (1/χ) against temperature curves is plotted to identify the magnetic contribution. Those curves indicate that the substitution of Ho into the ZnO compound causes a weaker antiferromagnetic (AFM) interaction.

  14. Application of FTIR Absorption Spectroscopy to Characterize Waste and Biofuels for Pyrolysis and Gasification

    KALISZ Sylwester; Svoboda, Karel; ROBAK Zbigniew; Baxter, David; Andersen, Lars

    2008-01-01

    The paper discusses the various applications of FTIR absorption spectroscopy as a tool for characterizing waste biofuels for pyrolysis and gasification. The FTIR spectrometer used in the study allows for analysis of solid and liquid waste and biofuel samples. Further, an attached dedicated gas cell is used in the characterization of gases evolving during pyrolysis in a versatile pyrolyser/gasifier attached to the FTIR. The pyrolyser operates in a batch mode and generates large quantities o...

  15. Self-absorption influence on the optical spectroscopy of zinc oxide laser produced plasma

    De Posada, E; Arronte, M A; Ponce, L; Rodriguez, E; Flores, T [Centro de Investigacion en Ciencia Aplicada y TecnologIa Avanzada-Unidad Altamira, Tamaulipas (Mexico); Lunney, J G, E-mail: edeposada@ipn.mx [School of Physics, Trinity College Dublin (Ireland)

    2011-01-01

    Optical spectroscopy is used to study the laser ablation process of ZnO targets. It is demonstrated that even if Partial Local Thermal Equilibrium is present, self absorption process leads to a decrease of recorded lines emission intensities and have to be taken into account to obtain correct values of such parameters. It is presented a method that combines results of both Langmuir probe technique and Anisimov model to obtain correct values of plasma parameters.

  16. Shock-Tube Measurement of Acetone Dissociation Using Cavity-Enhanced Absorption Spectroscopy of CO.

    Wang, Shengkai; Sun, Kai; Davidson, David F; Jeffries, Jay B; Hanson, Ronald K

    2015-07-16

    A direct measurement for the rate constant of the acetone dissociation reaction (CH3COCH3 = CH3CO + CH3) was conducted behind reflected shock wave, utilizing a sub-ppm sensitivity CO diagnostic achieved by cavity-enhanced absorption spectroscopy (CEAS). The current experiment eliminated the influence from secondary reactions and temperature change by investigating the clean pyrolysis of shock-tube kinetics studies.

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

    Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

    2013-11-04

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

  18. Determination of Aluminum Concentration in Seawater by Colorimetry and Atomic Absorption Spectroscopy.

    1972-11-30

    this was also high. 5 . ,Irj ~ - • lri*; llo. TALLE 2 ATOMIC ABSORPTION SPECTROSCOPY DETEPIJINATION OF ALUMINU1 CONCENTRATIO11 OF SEAWATER OCEAN...Concentration in Seawater by Colorimetr-y and Atomic Absorption Spectroscopy Charles A. Greene, Jr. and Everett N. Jones Ocean Science Department T14

  19. Study of the L{sub 2,3} edges of 3d transition metals by X-ray absorption spectroscopy

    Akguel, G. [Physics Department, University of Cukurova, 01330 Adana (Turkey); Aksoy, F. [Physics Department, University of Cukurova, 01330 Adana (Turkey); Physics Department, University of Nigde, 51100 Nigde (Turkey); Bozduman, A.; Ozkendir, O.M. [Physics Department, University of Cukurova, 01330 Adana (Turkey); Ufuktepe, Y. [Physics Department, University of Cukurova, 01330 Adana (Turkey)], E-mail: ufuk@cu.edu.tr; Luening, J. [Universite Pierre and Marie Curie, Laboratoire de Chimie Physique-Matiere et Rayonnement 75231 Paris (France)

    2008-11-28

    In the soft X-rays energy region, near edge X-ray absorption fine structure (NEXAFS) spectra are generally recorded by monitoring yield signals of secondary particles. These secondary particles, electrons or fluorescence photons, follow from the decay of the core hole excited in the primary absorption process. In general the yield signals are, to a good approximation, proportional to the absorption coefficient. However, in several applications it would be desirable to measure the absorption coefficient quantitatively. To derive the absorption coefficient quantitatively from a yield spectrum, one needs to know the escape depth of the emitted electrons ({lambda}{sub e}) of the applied yield technique in the material of interest. Since this quantity is difficult to calculate, it is unknown for most materials. In this paper we present the first results of our systematic investigation of the total electron-yield (TEY) escape depth of the 3d transition metals (Fe, Co and Cu). In addition our results gave important information on the variation of the TEY escape depth with the filling of the 3d band.

  20. Determination of copper, zinc and iron in broncho-alveolar lavages by atomic absorption spectroscopy.

    Harlyk, C; Mccourt, J; Bordin, G; Rodriguez, A R; van der Eeckhout, A

    1997-11-01

    Concentrations of Zn, Cu and Fe were measured in 157 broncho-alveolar lavages (BAL), before and after centrifugation, collected at the Leuven University Hospital (Belgium). Zn was measured by flame-atomic absorption spectroscopy, using direct calibration, while Cu and Fe were determined by electrothermal atomic absorption spectroscopy, using the method of standard additions. For Fe only 56 samples were measured. Most of the studied elements are present in the liquid phase (supernatant). About 90% of Cu concentrations lie between 0 and 15 micrograms/kg, while 90% of Zn concentrations are lower than 230 micrograms/kg, with 30% between 30 and 70 micrograms/kg, and 50% between 100 and 200 micrograms/kg. There seems to be a reverse relationship between Cu and Zn levels with high Cu going along with low Zn and vice versa.

  1. Galactic Outflows in Absorption and Emission: Near-UV Spectroscopy of Galaxies at 1

    Erb, Dawn K; Henry, Alaina L; Martin, Crystal L

    2012-01-01

    We study large-scale outflows in a sample of 96 star-forming galaxies at 1spectroscopy of FeII and MgII absorption and emission. The average blueshift of the FeII interstellar absorption lines with respect to the systemic velocity is -85+/-10 km/s at z~1.5, with standard deviation 87 km/s; this is a decrease of a factor of two from the average blueshift measured for far-UV interstellar absorption lines in similarly selected galaxies at z~2. The profiles of the MgII 2796, 2803 lines show much more variety than the FeII profiles, which are always seen in absorption; MgII ranges from strong emission to pure absorption, with emission more common in galaxies with blue UV slopes and at lower stellar masses. Outflow velocities, as traced by the centroids and maximum extent of the absorption lines, increase with increasing stellar mass with 2-3sigma significance, in agreement with previous results. We study fine structure emission from FeII*, finding several lines of evidence in support of t...

  2. Coelectrodeposition of Ternary Mn-Oxide/Polypyrrole Composites for ORR Electrocatalysts: A Study Based on Micro-X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping

    Benedetto Bozzini

    2015-08-01

    Full Text Available Low energy X-ray fluorescence (XRF and soft X-ray absorption (XAS microspectroscopies at high space-resolution are employed for the investigation of the coelectrodeposition of composites consisting of a polypyrrole(PPy-matrix and Mn-based ternary dispersoids, that have been proposed as promising electrocatalysts for oxygen-reduction electrodes. Specifically, we studied Mn–Co–Cu/PP, Mn–Co–Mg/PPy and Mn–Ni–Mg/PPy co-electrodeposits. The Mn–Co–Cu system features the best ORR electrocatalytic activity in terms of electron transfer number, onset potential, half-wave potential and current density. XRF maps and micro-XAS spectra yield compositional and chemical state distributions, contributing unique molecular-level information on the pulse-plating processes. Mn, Ni, Co and Mg exhibit a bimodal distribution consisting of mesoscopic aggregates of micrometric globuli, separated by polymer-rich ridges. Within this common qualitative scenario, the individual systems exhibit quantitatively different chemical distribution patterns, resulting from specific electrokinetic and electrosorption properties of the single components. The electrodeposits consist of Mn3+,4+-oxide particles, accompanied by combinations of Co0/Co2+, Ni0/Ni2+ and Cu0,+/Cu2+ resulting from the alternance of cathodic and anodic pulses. The formation of highly electroactive Mn3+,4+ in the as-fabricated material is a specific feature of the ternary systems, deriving from synergistic stabilisation brought about by two types of bivalent dopants as well as by galvanic contact to elemental metal; this result represents a considerable improvement in material quality with respect to previously studied Mn/PPy and Mn-based/PPy binaries.

  3. Photochemistry of Wild-Type and N378D Mutant E. coli DNA Photolyase with Oxidized FAD Cofactor Studied by Transient Absorption Spectroscopy.

    Müller, Pavel; Brettel, Klaus; Grama, Laszlo; Nyitrai, Miklos; Lukacs, Andras

    2016-05-04

    DNA photolyases (PLs) and evolutionarily related cryptochrome (CRY) blue-light receptors form a widespread superfamily of flavoproteins involved in DNA photorepair and signaling functions. They share a flavin adenine dinucleotide (FAD) cofactor and an electron-transfer (ET) chain composed typically of three tryptophan residues that connect the flavin to the protein surface. Four redox states of FAD are relevant for the various functions of PLs and CRYs: fully reduced FADH(-) (required for DNA photorepair), fully oxidized FADox (blue-light-absorbing dark state of CRYs), and the two semireduced radical states FAD(.-) and FADH(.) formed in ET reactions. The PL of Escherichia coli (EcPL) has been studied for a long time and is often used as a reference system; however, EcPL containing FADox has so far not been investigated on all relevant timescales. Herein, a detailed transient absorption study of EcPL on timescales from nanoseconds to seconds after excitation of FADox is presented. Wild-type EcPL and its N378D mutant, in which the asparagine facing the N5 of the FAD isoalloxazine is replaced by aspartic acid, known to protonate FAD(.-) (formed by ET from the tryptophan chain) in plant CRYs in about 1.5 μs, are characterized. Surprisingly, the mutant protein does not show this protonation. Instead, FAD(.-) is converted in 3.3 μs into a state with spectral features that are different from both FADH(.) and FAD(.-) . Such a conversion does not occur in wild-type EcPL. The chemical nature and formation mechanism of the atypical FAD radical in N378D mutant EcPL are discussed.

  4. Contribution of multielectron excitation to F 1s photoabsorption process in CaF{sub 2} studied by soft X-ray absorption and emission spectroscopy

    Oura, M. [RIKEN/SPring-8, Harima Institute, 1-1-1 Kouto, Mikazuki, Sayo, Hyogo 679-5148 (Japan)]. E-mail: oura@spring8.or.jp; Taguchi, M. [RIKEN/SPring-8, Harima Institute, 1-1-1 Kouto, Mikazuki, Sayo, Hyogo 679-5148 (Japan); Mukoyama, T. [Kansai Gaidai University, 16-1 Nakamiya-Higashino-cho, Hirakata, Osaka 573-1001 (Japan); Takeuchi, T. [RIKEN/SPring-8, Harima Institute, 1-1-1 Kouto, Mikazuki, Sayo, Hyogo 679-5148 (Japan); Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601 (Japan); Shin, S. [RIKEN/SPring-8, Harima Institute, 1-1-1 Kouto, Mikazuki, Sayo, Hyogo 679-5148 (Japan); ISSP/University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan)

    2005-06-15

    The photoexcited F K{alpha} X-ray intensity's evolution was measured for CaF{sub 2} with fine energy-step from the [1s2p] double excitation threshold to the saturation region, where square brackets indicate hole states. The observed evolution was directly compared with the X-ray absorption spectrum, and the contribution of multielectron excitation to the absorption spectrum was successfully resolved. The F-K fluorescence XANES spectra were calculated based on the coherent second-order optical processes for comparison.

  5. X-RAY ABSORPTION SPECTROSCOPY OF YB3+-DOPED OPTICAL FIBERS

    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.

  6. Usage of X-ray absorption spectroscopy and extractive fractionation in studies of the Cu (II and Zn (II ions in soils

    Dina Nevidomskaya

    2014-12-01

    Full Text Available XANES spectroscopy is an effective method for the study of bonds between metals and soil components. The study of structural organization in different soil samples and soil phases saturated with Cu2+ and Zn2+ ions by using XANES allowed determining the mechanism of their interaction with soil phases and all the chemical bindings taken place in the course of this process. Changes in the structure of the metal ion, in particular breakdown of the symmetry of electron orbits of atoms, take place due to interaction with soil components. Application of this method demonstrated that the state of copper and zinc introduced in chernozem as oxides did not change after one year of incubation. Copper is absorbed after being introduced as soluble salts, and copper ions are incorporated in the octahedral and tetrahedral sites of minerals and bonded with humic materials at the expense of covalent bond and the formation of coordination humate copper complexes. Zinc included into octahedric structures of layered minerals and hydro(oxides can be inner-and outer-sphere adsorbed. It is shown that the action of the metal bound to soil components becomes weakened in case of increasing the Cu and Zn load (from 2000 to 10000 mg/kg especially applied in the form of soluble salts. Extractive fractionation of metal compounds in chernozem samples, artificially contaminated with copper and zinc salts serves as evidence of absorbing the applied Cu2+ ions by the soil organic matter and Zn2+ ions – by silicates, carbonates, and Fe-Mn oxides.

  7. [Measurement of nonuniform temperature and concentration distribution by absorption spectroscopy based on least-square fitting].

    Song, Jun-Ling; Hong, Yan-Ji; Wang, Guang-Yu; Pan, Hu

    2013-08-01

    The measurement of nonuniform temperature and concentration distributions was investigated based on tunable diode laser absorption spectroscopy technology. Through direct scanning multiple absorption lines of H2O, two zones for temperature and concentration distribution were achieved by solving nonlinear equations by least-square fitting from numerical and experimental studies. The numerical results show that the calculated temperature and concentration have relative errors of 8.3% and 7.6% compared to the model, respectively. The calculating accuracy can be improved by increasing the number of absorption lines and reduction in unknown numbers. Compared with the thermocouple readings, the high and low temperatures have relative errors of 13.8% and 3.5% respectively. The numerical results are in agreement with the experimental results.

  8. Green biochemistry approach for synthesis of silver and gold nanoparticles using Ficus racemosa latex and their pH-dependent binding study with different amino acids using UV/Vis absorption spectroscopy.

    Tetgure, Sandesh R; Borse, Amulrao U; Sankapal, Babasaheb R; Garole, Vaman J; Garole, Dipak J

    2015-04-01

    Simple and eco-friendly biosynthesis approach was developed to synthesize silver nanoparticles (SNPs) and gold nanoparticles (GNPs) using Ficus racemosa latex as reducing agent. The presence of sunlight is utilized with latex and achieved the nanoparticles whose average size was in the range of 50-120 nm for SNPs and 20-50 nm for GNPs. The synthesized nanoparticles were characterized by UV/Visible absorption spectroscopy, X-ray diffraction, and field emission-scanning electron microscopy techniques toget understand the obtained nanoparticles. The pH-dependent binding studies of SNPs and GNPs with four amino acids, namely L-lysine, L-arginine, L-glutamine and glycin have been reported.

  9. Pseudocapacitance of MnO{sub 2} originates from reversible insertion/desertion of thiocyanate anions studied using in situ X-ray absorption spectroscopy in ionic liquid electrolyte

    Lee, Ming-Tsung; Tsai, Wen-Ta; Chang, Jeng-Kuei [Department of Materials Science and Engineering, National Cheng Kung University, 1 University Road, Tainan (China); Deng, Ming-Jay; Cheng, Hui-Fang; Sun, I-Wen [Department of Chemistry, National Cheng Kung University, 1 University Road, Tainan (China)

    2010-02-01

    Charge storage mechanisms of electrodeposited MnO{sub 2} in various aprotic ionic liquids (ILs) are studied using in situ X-ray absorption spectroscopy (XAS). The analytical results show that a unique thiocyanate (SCN{sup -}) anion can reversibly insert/desert into/from the tunnels between the [MnO{sub 6}] octahedral subunits depending on the applied potential. This process charge compensates the Mn{sup 3+}/Mn{sup 4+} redox transition upon charging-discharging and thus contributes to an ideal pseudocapacitive behavior of the MnO{sub 2} electrode. The present work would open up a route for developing a novel oxide-based supercapacitor, with high cell-voltage, high thermal stability, and high safety, incorporating IL electrolytes. (author)

  10. Characteristic absorption peak of the human blood measured with differential photoacoustic spectroscopy

    2002-01-01

    A new highly sensitive spectroscopy technique- differential photoacoustic spectroscopy (PAS) is presented in this paper. The blood samples from 3 healthy persons, patients with leukemia, patients with pregnancy-induced hypertension (PIH), and 40 patients with nasopharyngeal carcinoma were measured by the PAS technique. The normalized, the first order, and the second order differential photoacoustic spectroscopy of the blood were gained. The results show that (ⅰ) weak absorption peaks or shoulder peaks, which could not be found using conventional photoacoustic spectroscopy, were determined by the first order and the second order differential photoacoustic spectroscopy which significantly improve the sensitivity of detection; and (ii) that two characteristic absorption peaks were found at the wavelength of 637 and 664 nm in all persons' blood samples by the differential photoacoustic spectroscopy technique. This experiment concludes that the differential photoacoustic spectroscopy technique is superior to the conventional photoacoustic spectroscopy technique in detecting photoacoustic spectroscopy of biological samples.

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

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

    2011-08-23

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

  12. Trace species detection in the near infrared using Fourier transform broadband cavity enhanced absorption spectroscopy: initial studies on potential breath analytes.

    Denzer, W; Hancock, G; Islam, M; Langley, C E; Peverall, R; Ritchie, G A D; Taylor, D

    2011-02-21

    Cavity enhanced absorption measurements have been made of several species that absorb light between 1.5 and 1.7 µm using both a supercontinuum source and superluminescent light emitting diodes. A system based upon an optical enhancement cavity of relatively high finesse, consisting of mirrors of reflectivity ∼99.98%, and a Fourier transform spectrometer, is demonstrated. Spectra are recorded of isoprene, butadiene, acetone and methane, highlighting problems with spectral interference and unambiguous concentration determinations. Initial results are presented of acetone within a breath-like matrix indicating ppm precision at absorption coefficient of ∼4 × 10(-9) cm(-1) reported within a 4 min acquisition time. Finally, two superluminescent light emitting diodes are coupled together to increase the wavelength coverage, and measurements are made simultaneously on acetylene, CO(2), and butadiene. The absorption cross-sections for acetone and isoprene have been measured with an instrumental resolution of 4 cm(-1) and are found to be 1.3 ± 0.1 × 10(-21) cm(2) at a wavelength of 1671.9 nm and 3.6 ± 0.2 × 10(-21) cm(2) at 1624.7 nm, respectively.

  13. Adsorption of Uranyl ions on Amine-functionalization of MIL-101(Cr) Nanoparticles by a Facile Coordination-based Post-synthetic strategy and X-ray Absorption Spectroscopy Studies.

    Zhang, Jian-Yong; Zhang, Na; Zhang, Linjuan; Fang, Yongzheng; Deng, Wei; Yu, Ming; Wang, Ziqiang; Li, Lina; Liu, Xiyan; Li, Jingye

    2015-09-10

    By a facile coordination-based post-synthetic strategy, the high surface area MIL-101(Cr) nanoparticles was functionallized by grafting amine group of ethylenediamine (ED) on coordinatively unsaturated Cr(III) centers, yielding a series of ED-MIL-101(Cr)-based adsorbents and their application for adsorption of U(VI) from aqueous solution were also studied. The obtained ED-functionallized samples with different ED contents were characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), FTIR, elemental analysis (EA) and N2 adsorption and desorption isothermal. Compared with the pristine MIL-101(Cr) sorbents, the ED-functionallized MIL-101(Cr) exhibits significantly higher adsorption capacity for U(VI) ions from water with maximum adsorption capacities as high as 200 mg/g (corresponding to 100% extraction rate) at pH of 4.5 with ED/Cr ratio of 0.68 and the sorbed U(VI) ions can easily be desorbed at lower pH (pH ≤ 2.0). The adsorption mode of U(VI) ions and effects of grafted ED on the MIL-101(Cr) frameworks were also been studied by X-ray absorption spectroscopy (XAS). We believe that this work establishes a simple and energy efficient route to a novel type of functional materials for U(VI) ions extraction from solution via the post-synthetic modification (PSM) strategy.

  14. New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.

    Zaera, Francisco

    2014-11-21

    Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are

  15. Ultraviolet photochemical reaction of [Fe(III)(C2O4)3](3-) in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser.

    Ogi, Y; Obara, Y; Katayama, T; Suzuki, Y-I; Liu, S Y; Bartlett, N C-M; Kurahashi, N; Karashima, S; Togashi, T; Inubushi, Y; Ogawa, K; Owada, S; Rubešová, M; Yabashi, M; Misawa, K; Slavíček, P; Suzuki, T

    2015-05-01

    Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III) oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3 eV and 200 fs, respectively. A femtosecond 268 nm pulse was employed to excite [Fe(III)(C2O4)3](3-) in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s), and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268 nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4 eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III)(C2O4)3](3-). The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III) is upon excitation immediately photoreduced to Fe(II), followed by ligand dissociation from Fe(II). Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO2 (•))Fe(II)(C2O4)2](3-) and subsequently [Fe(II)(C2O4)2](2-).

  16. Ultraviolet photochemical reaction of [Fe(III(C2O43]3− in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser

    Y. Ogi

    2015-05-01

    Full Text Available Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3 eV and 200 fs, respectively. A femtosecond 268 nm pulse was employed to excite [Fe(III(C2O43]3− in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s, and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268 nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4 eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III(C2O43]3−. The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III is upon excitation immediately photoreduced to Fe(II, followed by ligand dissociation from Fe(II. Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO2•Fe(II(C2O42]3− and subsequently [Fe(II(C2O42]2−.

  17. Photo-induced absorption in the pump probe spectroscopy of single-walled carbon nanotubes

    Zhu Zi-Peng

    2013-01-01

    Femtosecond pump probe spectroscopy is employed to study the photo-induced absorption feature in the singlewalled carbon nanotube transient spectrum.The two advantages of the experiment,a chirality enriched sample and tuning the pump wavelength to the resonance of a specific nanotube species,greatly facilitate the identification of the photoinduced absorption signal of one tube species.It is found that a photo-induced absorption feature is located at one radial breathing mode to the blue side of the Eii state.This finding prompts a new explanation for the origin of the photoinduced absorption:the transition from the ground state to a phonon coupled state near the Eii state.The explanation suggests a superposition mechanism of the photo-bleach and photo-induced absorption signals,which may serve as a key to the interpretation of the complex pump probe transient spectrum of carbon nanotubes.The finding sheds some light on the understanding of the complex non-radiative relaxation process and the electronic structure of single-walled carbon nanotubes.

  18. Unoccupied density of states of La2–xSrxNiO4+δ studied by polarization-dependent x-ray-absorption spectroscopy and bremsstrahlung isochromat spectroscopy

    Kuiper, P.; Elp, J. van; Sawatzky, G.A.; Fujimori, A.; Hosoya, S.; Leeuw, D.M. de

    1991-01-01

    Oxygen 1s x-ray-absorption measurements of La2–xSrxNiO4+δ (0≤x≤1.15) are presented, together with O 1s polarization-dependent x-ray absorption on single-crystal La1.85Sr0.15NiO4. It is concluded that the charge-compensating holes have mainly oxygen 2p character. The Ni 3d9 final states reached becau

  19. Near Infrared Cavity Enhanced Absorption Spectroscopy Study of N2 O%N2 O的近红外腔增强吸收光谱技术研究

    吴志伟; 董燕婷; 周卫东

    2014-01-01

    Using a tunable near infrared external cavity diode laser and a 650mm long high finesse optical cavity consisting of two highly reflective (R= 99. 97% at 6 561. 39 cm-1 )plan-concave mirrors of curvature radius ~1 000 mm,a cavity enhanced ab-sorption spectroscopy (CEAS)system was made.The absorption spectra centered at 6 561. 39 cm-1 of pure N2 O gas and gas mixtures of N2 O and N2 were recorded.According to the absorption of N2 O at 6 561. 39 cm-1 in the cavity,the measured effec-tive absorption path was about 1 460 km.The spectra line intensity and line-width of N2 O centered at 6 561. 39 cm-1 were care-fully studied.The relationship between the line-width of absorption spectra and the gas pressure was derived.The pressure broadening parameter of N2 gas for N2O line centered at 6 561. 39 cm-1 was deduced and given a value of ~(0. 114±0. 004) cm-1 ·atm-1 .The possibility to detect trace N2 O gas in mixture using this CEAS system was investigated.By recording the ab-sorption spectra of N2 O gas mixtures at different concentration,the relationship between the line intensity and gas concentration was derived.The minimum detectable absorption was found to be 2. 34×10-7 cm-1 using this cavity enhanced absorption spec-troscopy system.And te measurement precision in terms of relative standard deviation (RSD)for N2 O is ~1. 73%,indicating the possibility of using the cavity enhanced absorption spectroscopy system for micro gas N2 O analysis in the future.%以外腔式可调谐、窄线宽近红外半导体激光为光源,以一对曲率半径r=1000 mm 的宽带高反射率平凹镜(反射率R=99.97%)构成的腔长为650 mm的对称高精度光学稳定腔,建立了腔增强吸收光谱系统。详细研究了纯净 N2 O 气体、以及 N2 O 和 N2的混合气体在不同浓度和不同气压下、中心波长位于6561.39 cm-1的腔增强吸收光谱、光谱强度和谱线宽度,该腔增强吸收光谱系统的有效吸收光程可达1460 km。

  20. Wavelength modulation spectroscopy--digital detection of gas absorption harmonics based on Fourier analysis.

    Mei, Liang; Svanberg, Sune

    2015-03-20

    This work presents a detailed study of the theoretical aspects of the Fourier analysis method, which has been utilized for gas absorption harmonic detection in wavelength modulation spectroscopy (WMS). The lock-in detection of the harmonic signal is accomplished by studying the phase term of the inverse Fourier transform of the Fourier spectrum that corresponds to the harmonic signal. The mathematics and the corresponding simulation results are given for each procedure when applying the Fourier analysis method. The present work provides a detailed view of the WMS technique when applying the Fourier analysis method.

  1. The influence of magnetic fields on absorption and emission spectroscopy

    Zhang, Heshou; Richter, Philipp

    2016-01-01

    Spectroscopic observations play essential roles in astrophysics. They are crucial for determining important physical parameters, providing information about the composition of various objects in the universe, as well as depicting motions in the universe. However, spectroscopic studies often do not consider the influence of magnetic fields. In this paper, we explore the influence of magnetic fields on the spectroscopic observations arising from Ground State Alignment (GSA). Synthetic spectra are generated to show the measurable changes of the spectra due to GSA. The influences of atomic alignment on absorption from DLAs, emission from H\\,{\\sc ii} Regions, submillimeter fine-structure lines from star forming regions are presented as examples to illustrate the effect in diffuse gas. Furthermore, we demonstrate the influence of atomic alignment on physical parameters derived from spectral line ratios, such as the alpha-to-iron ratio([X/Fe]), interstellar temperature, and ionization rate. Results in our paper show...

  2. VUV Absorption Spectroscopy of Planetary Molecules at Low Temperature

    Jolly, A.; Benilan, Y.; Ferradaz, T.; Fray, N.; Schwell, M.

    2005-08-01

    A critical review of the available absorption coefficient in the vacuum ultraviolet domain (100-200 nm) has lead us to undertake new measurements at the Berlin synchrotron facility (BESSY). Many of the molecules detected in planetary atmospheres and in particular those which need to be synthesized in the laboratory, have never been measured at low temperature. The first molecules that we have studied are HCN, HC3N and C2N2. New absorption coefficients have been obtained including first spectra at low temperature (220 K). The effect of the temperature on the spectra can then be discussed in view of the application to the much colder atmosphere of Titan. The nitriles studied here play an important role in the chemistry taking place in Titan's atmosphere and are believed to be responsible for the formation of Titan's aerosols. From our measurements, we have calculated the photodissociation rates for each molecule which are essential to include in any photochemical model. This is true for Titan but also for cometary and interstellar medium models. To describe the formation of a solid phase, the models also need to include photodissociation rates for larger molecules which have not been detected yet. This will now be possible for HC5N since the first spectra of this molecule has been obtained by our team. Furthermore, the first stellar occultation measurement of Titan's atmosphere by the UV spectrometer (UVIS) on board the CASSINI spacecraft has permitted the detection of species not observed before in this wavelength domain. But it has also shown a lack of experimental data in this domain. So far, the model is not able to reproduce the observed spectral feature. C4H2 is the molecule that should explain some of the observed feature but absolute cross sections are missing. We will present our latest experimental measurements on this molecule.

  3. Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

    Pendleton, Y. J.; Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Sellgren, K.

    1994-01-01

    We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous

  4. Single metal nanoparticle absorption spectroscopy and optical characterization

    Muskens, O. L.; Del Fatti, N.; Vallée, F.; Huntzinger, J. R.; Billaud, P.; Broyer, M.

    2006-02-01

    Optical absorption spectra of small single metal nanoparticles are measured using a far-field technique combining a spatial modulation microscope with a broadband light source. Quantitative determination of the spectral and polarization dependencies of the absorption cross section of individual gold nanoparticles permits precise determination of their geometrical properties in excellent agreement with transmission electron microscopy measurements.

  5. Low Field Zeeman Magnetometry Using Rubidium Absorption Spectroscopy

    Ram, Nibedita; Pattabiraman, M; Vijayan, C [Department of Physics, Indian Institute of Technology, Madras, Chennai 600036 (India)

    2007-09-15

    We report on the feasibility of utilizing the field dependence of the Doppler-free unresolved absorption line amplitude of Rubidium vapour for magnetic field measurements for fields below 50 G. The field dependence of the saturation absorption and Doppler broadened fluorescence line amplitudes have been systematically analyzed by computing the hyperfine energy eigenvalues and the transition probability among the Zeeman sublevels.

  6. Exploring electrosorption at iron electrode with in situ surface-enhanced infrared absorption spectroscopy.

    Huo, Sheng-Juan; Wang, Jin-Yi; Yao, Jian-Lin; Cai, Wen-Bin

    2010-06-15

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) in attenuated total reflection (ATR) configuration has been extended to the Fe electrode/electrolyte interface in neutral and weakly acidic solutions for the first time. The SEIRA-active Fe film electrode was obtained through a potentiostatic electrodeposition of a virtually pinhole-free 40 nm-thick Fe overfilm onto a 60 nm-thick Au underfilm chemically predeposited on the reflecting plane of an ATR Si prism. The infrared absorption for CO adlayer at the Fe film electrode measured with ATR-SEIRAS was enhanced by a factor of larger than 34, as compared to that at a Fe bulk electrode with external infrared absorption spectroscopy in the literature. More importantly, the unipolar band shape enabled the reliable determination of the Stark tuning rates of CO adlayer at Fe electrode. In situ ATR-SEIRAS was also applied to study the electrosorption of a typical corrosion inhibitor benzotriazole (BTAH) on Fe electrode as a function of potential, providing additional spectral information at positive potentials in support of the formation of a polymer-like surface complex Fe(II)(m)(BTA)(n) as the corrosion-resistant layer.

  7. Infrared absorption spectroscopy of hydrogen-related defects in ZnO

    Lavrov, E.V

    2003-12-31

    Most of the ZnO growth techniques result in n-type conductivity of the crystal, which hinders the progress of ZnO applications for electronic devices. Hydrogen incorporated during the process of crystal growth is now considered as a likely source of the n-type conductivity of ZnO. Infrared absorption spectroscopy provides detailed insights into the physical properties of the light impurities in semiconductor matrix and is, therefore, an excellent tool to explore the structure of the hydrogen-related defects embedded in ZnO. We report on a number of hydrogen-related defects observed in hydrothermal grown ZnO and ZnO grown from the vapor phase studied by Fourier transform infrared absorption spectroscopy. Three IR absorption lines at 3611.3, 3349.6 and 3312.2 cm{sup -1} at 10 K are observed after hydrogenation of the vapor phase grown ZnO. The line at 3611.3 cm{sup -1} is tentatively assigned to a bond-centered H, whereas the other two are identified as a Zn vacancy decorated with two H atoms. A Ni-H complex with a H atom primarily bound to oxygen is suggested to be responsible for the 3577.3 cm{sup -1} line observed at 10 K in as-grown hydrothermal ZnO.

  8. [Signal analysis and spectrum distortion correction for tunable diode laser absorption spectroscopy system].

    Bao, Wei-Yi; Zhu, Yong; Chen, Jun; Chen, Jun-Qing; Liang, Bo

    2011-04-01

    In the present paper, the signal of a tunable diode laser absorption spectroscopy (TDLAS) trace gas sensing system, which has a wavelength modulation with a wide range of modulation amplitudes, is studied based on Fourier analysis method. Theory explanation of spectrum distortion induced by laser intensity amplitude modulation is given. In order to rectify the spectrum distortion, a method of synchronous amplitude modulation suppression by a variable optical attenuator is proposed. To validate the method, an experimental setup is designed. Absorption spectrum measurement experiments on CO2 gas were carried out. The results show that the residual laser intensity modulation amplitude of the experimental system is reduced to -0.1% of its original value and the spectrum distortion improvement is 92% with the synchronous amplitude modulation suppression. The modulation amplitude of laser intensity can be effectively reduced and the spectrum distortion can be well corrected by using the given correction method and system. By using a variable optical attenuator in the TDLAS (tunable diode laser absorption spectroscopy) system, the dynamic range requirements of photoelectric detector, digital to analog converter, filters and other aspects of the TDLAS system are reduced. This spectrum distortion correction method can be used for online trace gas analyzing in process industry.

  9. Medieval glass from the Cathedral in Paderborn: a comparative study using X-ray absorption spectroscopy, X-ray fluorescence, and inductively coupled laser ablation mass spectrometry

    Hormes, J. [University of Saskatchewan, Canadian Light Source Inc., Saskatoon, SK (Canada); Louisiana State University, CAMD, Baton Rouge, LA (United States); Roy, A.; Bovenkamp, G.L. [Louisiana State University, CAMD, Baton Rouge, LA (United States); Simon, K. [University of Goettingen, Geochemistry, Centre for Geosciences, Goettingen (Germany); Kim, C.Y. [University of Saskatchewan, Canadian Light Source Inc., Saskatoon, SK (Canada); Boerste, N. [Faculty for Theology Paderborn, Paderborn (Germany); Gai, S. [LWL - Archaeologie fuer Westfalen, Muenster (Germany)

    2013-04-15

    We have investigated four stained glass samples recovered from an archaeological excavation at the Cathedral in Paderborn (Germany) between 1978 and 1980. On two of the samples there are parts of paintings. Concentrations of major elements were determined using two independent techniques: LA-ICP-MS (a UV laser ablation microsampler combined with an inductively coupled plasma mass spectrometer) and synchrotron radiation X-ray excited X-ray fluorescence (SR-XRF). The SR-XRF data were quantified by using the program package PyMCA developed by the software group of the ESRF in Grenoble. Significant differences were found between the concentrations determined by the two techniques that can be explained by concentration gradients near the surface of the glasses caused, for example, by corrosion/leaching processes and the different surface sensitivities of the applied techniques. For several of the elements that were detected in the glass and in the colour pigments used for the paintings X-ray absorption near edge structure (XANES) spectra were recorded in order to determine the chemical speciation of the elements of interest. As was expected, most elements in the glass were found as oxides in their most stable form. Two notable exceptions were observed: titanium was not found as rutile - the most stable form of TiO{sub 2} - but in the form of anatase, and lead was not found in one defined chemical state but as a complex mixture of oxide, sulphate, and other compounds. (orig.)

  10. Theoretical analysis on two-photon absorption spectroscopy in a confined four-level atomic system

    Yuanyuan Li; Jintao Bai; Li Li; Yanpeng Zhang; Xun Hou

    2009-01-01

    We investigate theoretically two-photon absorption spectroscopy modified by a control field in a confined Y-type four-level system. Dicke-narrowing effect occurs both in two-photon absorption lines and the dips of transparency against two-photon absorption due to enhanced contribution of slow atoms. We also find that the suppression and the enhancement of two-photon absorption can be modified by changing the strength of the control field and the detuning of three laser fields. This control of two-photon absorption may have some applications in information processing and optical devices.

  11. Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

    Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

    2017-01-01

    Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.

  12. VUV absorption spectroscopy of bacterial spores and DNA components

    Fiebrandt, Marcel; Lackmann, Jan-Wilm; Raguse, Marina; Moeller, Ralf; Awakowicz, Peter; Stapelmann, Katharina

    2017-01-01

    Low-pressure plasmas can be used to inactivate bacterial spores and sterilize goods for medical and pharmaceutical applications. A crucial factor are damages induced by UV and VUV radiation emitted by the plasma. To analyze inactivation processes and protection strategies of spores, absorption spectra of two B. subtilis strains are measured. The results indicate, that the inner and outer coat of the spore significantly contribute to the absorption of UV-C and also of the VUV, protecting the spore against radiation based damages. As the sample preparation can significantly influence the absorption spectra due to salt residues, the cleaning procedure and sample deposition is tested for its reproducibility by measuring DNA oligomers and pUC18 plasmid DNA. The measurements are compared and discussed with results from the literature, showing a strong decrease of the salt content enabling the detection of absorption structures in the samples.

  13. Saturation dynamics and working limits of saturated absorption cavity ringdown spectroscopy.

    Sadiek, Ibrahim; Friedrichs, Gernot

    2016-08-17

    Cavity ringdown spectroscopy (CRDS) in the linear absorption regime is a well-established method for sensitive trace gas detection, but only a few studies have addressed quantitative measurements in the presence of a saturated sample. In fact, saturation is usually avoided in order to escape from the required complex modeling of the saturation process that depends on the characteristics of the absorbing species, its interaction with the surrounding gas as well as on the temporal and spectral characteristics of the cavity excitation. Conversely, the novel saturated-absorption cavity ringdown spectroscopy approach (SCAR/Sat-CRDS) takes advantage of sample saturation in order to allow one to extract both the gas absorption and the empty cavity loss rates from a single ringdown event. Using a new continuous-wave infrared CRD spectrometer equipped with a tunable narrow-bandwidth high-power OPO laser system and a 18 bit digitizer, the transient dynamics of absorption saturation and the working limits of the Sat-CRDS approach in terms of its ability to extract reliable trace gas concentrations have been experimentally studied in this work. Using a strong methane transition as a test case, the excitation power P0 and saturation power PS have been systematically varied to explore a wide range of saturation regimes. At pressures 5 μbar γc, a pronounced coupling between the two parameters has been observed. Finally, a standard error analysis was performed revealing that the Sat-CRDS approach holds its advantages over conventional CRDS implementations in particular when the attainable ultimate detection sensitivity is limited by uncertainties in the empty cavity ringdown constant.

  14. Multiple scattering approach to X-ray absorption spectroscopy

    2003-01-01

    In this paper we present the state of the art of the theoretical background needed for analyzing X-ray absorption spectra in the whole energy range. The multiple-scattering (MS) theory is presented in detail with some applications on real systems. We also describe recent progress in performing geometrical fitting of the XANES (X-ray absorption near-edge structure) energy region and beyond using a full multiple-scattering approach.

  15. X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

    Yoo, Changhyeon

    In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

  16. High-Resolution Absorption Spectroscopy of NO2

    1987-08-31

    identify by block number) FIELD GROUP SUB-GROUP Atmospheric propagation, Laser spectroscopy, Nitrogen dioxide , Spectroscopy 19. RACT (Continue on reverse if...of this region is of interest for a number of reasons. The photodissociation of NO2 below 4200 A and the increasing presence of NO2 as an atmospheric...materials: metals, alloys, ceramics, polymers and their composites, aid new forms of carbon ; non- destructive evaluation, component failure analysis and

  17. In situ gas temperature measurements by UV-absorption spectroscopy

    Fateev, Alexander; Clausen, Sønnik

    2009-01-01

    The absorption spectrum of the NO A(2)Sigma(+) <- X(2)Pi gamma-system can be used for in situ evaluation of gas temperature. Experiments were performed with a newly developed atmospheric-pressure high-temperature flow gas cell at highly uniform and stable gas temperatures over a 0.533 m path in t....... The accuracy of both methods is discussed. Validation of the classical Lambert-Beer law has been demonstrated at NO concentrations up to 500 ppm and gas temperatures up to 1,500 degrees C over an optical absorption path length of 0.533 m.......The absorption spectrum of the NO A(2)Sigma(+) gas temperature. Experiments were performed with a newly developed atmospheric-pressure high-temperature flow gas cell at highly uniform and stable gas temperatures over a 0.533 m path...... in the range from 23 degrees C to 1,500 degrees C. The gas temperature was evaluated (1) from the analysis of the structure of selected NO high-resolution gamma-absorption bands and (2) from the analysis of vibrational distribution in the NO gamma-absorption system in the (211-238) nm spectral range...

  18. A transient absorption study of allophycocyanin

    Y J Shiu; J M Zhang; M Hayashi; V Gulbinas; C M Yang; S H Lin

    2002-12-01

    Transient dynamics of allophycocyanin trimers and monomers are observed by using the pump-probe, transient absorption technique. The origin of spectral components of the transient absorption spectra is discussed in terms of both kinetics and spectroscopy. We find that the energy gap between the ground and excited states of the unexcited subunit of allophycocyanin monomer decreases via an interaction with another excited subunit. For allophycocyanin trimer, we find that the fast dynamics results from the fast internal conversion and the first excited state is the only one electronic state which can trap the final population.

  19. Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

    Nielsen, Ulla Gro; Paik, Younkee; Julmis, Keinia;

    2005-01-01

    High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, th...

  20. Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

    Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.; Smith, Steven C.; McNamara, Bruce K.; Buck, Edgar C.; Eiden, Gregory C.; Duffin, Andrew M.

    2016-03-01

    Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS to study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.

  1. [The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

    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

  2. High-Resolution X-ray Emission and X-ray Absorption Spectroscopy

    de Groot, F. M. F.

    2001-01-01

    In this review, high-resolution X-ray emission and X-ray absorption spectroscopy will be discussed. The focus is on the 3d transition-metal systems. To understand high-resolution X-ray emission and reso-nant X-ray emission, it is first necessary to spend some time discussing the X-ray absorption process. Section II discusses 1s X-ray absorption, i.e., the K edges, and section III deals with 2p X-ray absorption, the L edges. X-ray emission is discussed in, respectively, the L edges. X-ray emis...

  3. Time-resolved pump-probe spectroscopy of intraband absorption by a semiconductor nanorod

    Leonov, Mikhail Y.; Rukhlenko, Ivan D.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-09-01

    We develop a theory of time-resolved pump-probe optical spectroscopy of intraband absorption of a probe pulse inside an anisotropic semiconductor nanorod. The absorption is preceded by the absorption of the pump pulse resonant to an interband transition. It is assumed that the resonantly exited states of the nanorod are interrelated via the relaxation induced by their interaction with a bath. We reveal the conditions for which the absorption of the probe's pulse is governed by a simple formula regardless of the pulse's shape. This formula is useful for the analysis of the experimental data containing information on the relaxation parameters of the nanorod's electronic subsystem.

  4. Initial Results of Optical Vortex Laser Absorption Spectroscopy in the HYPER-I Device

    Yoshimura, Shinji; Asai, Shoma; Aramaki, Mitsutoshi; Terasaka, Kenichiro; Ozawa, Naoya; Tanaka, Masayoshi; Morisaki, Tomohiro

    2015-11-01

    Optical vortex beams have a potential to make a new Doppler measurement, because not only parallel but perpendicular movement of atoms against the beam axis causes the Doppler shift of their resonant absorption frequency. As the first step of a proof-of-principle experiment, we have performed the optical vortex laser absorption spectroscopy for metastable argon neutrals in an ECR plasma produced in the HYPER-I device at the National Institute for Fusion Science, Japan. An external cavity diode laser (TOPTICA, DL100) of which center wavelength was 696.735 nm in vacuum was used for the light source. The Hermite-Gaussian (HG) beam was converted into the Laguerre-Gaussian (LG) beam (optical vortex) by a computer-generated hologram displayed on the spatial light modulator (Hamamatsu, LCOS-SLM X10468-07). In order to make fast neutral flow across the LG beam, a high speed solenoid valve system was installed on the HYPER-I device. Initial results including the comparison of absorption spectra for HG and LG beams will be presented. This study was supported by NINS young scientists collaboration program for cross-disciplinary study, NIFS collaboration research program (NIFS13KOAP026), and JSPS KAKENHI grant number 15K05365.

  5. Vacuum-UV absorption spectroscopy of interstellar ice analogues. III. Isotopic effects

    Cruz-Diaz, G. A.; Caro, G. M. Muñoz; Chen, Y.-J.

    2014-04-01

    This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave discharged hydrogen flow lamp as the VUV source. Prior to this work, we have recently submitted a similar study of the light isotopologues (Cruz-Diaz, Muñoz Caro & Chen). The VUV spectra are compared to those of the light isotopologues in the solid phase, and to the gas phase spectra of the same molecules. Our study is expected to improve very significantly the models that estimate the VUV absorption of ice mantles in space, which have often used the available gas phase data as an approximation of the absorption cross sections of the molecular ice components. We will show that this work has also important implications for the estimation of the photodesorption rates per absorbed photon in the ice.

  6. Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

    Wu, Yun; Li, Wei; Sparks, Donald L

    2015-11-17

    Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

  7. Combined characterization of bovine polyhemoglobin microcapsules by UV-Vis absorption spectroscopy and cyclic voltammetry.

    Knirsch, Marcos Camargo; Dell'Anno, Filippo; Salerno, Marco; Larosa, Claudio; Polakiewicz, Bronislaw; Eggenhöffner, Roberto; Converti, Attilio

    2017-03-01

    Polyhemoglobin produced from pure bovine hemoglobin by reaction with PEG bis(N-succynimidil succinate) as a cross-linking agent was encapsulated in gelatin and dehydrated by freeze-drying. Free carboxyhemoglobin and polyhemoglobin microcapsules were characterized by UV-Vis spectroscopy in the absorption range 450-650 nm and cyclic voltammetry in the voltage range from -0.8 to 0.6 mV to evaluate the ability to break the bond with carbon monoxide and to study the carrier's affinity for oxygen, respectively. SEM used to observe the shape of cross-linked gelatin-polyhemoglobin microparticles showed a regular distribution of globular shapes, with mean size of ~750 nm, which was ascribed to gelatin. Atomic absorption spectroscopy was also performed to detect iron presence in microparticles. Cyclic voltammetry using an Ag-AgCl electrode highlighted characteristic peaks at around -0.6 mV that were attributed to reversible oxygen bonding with iron in oxy-polyhemoglobin structure. These results suggest this technique as a powerful, direct and alternative method to evaluate the extent of hemoglobin oxygenation.

  8. X-ray absorption spectroscopy investigation of structurally modified lithium niobate crystals

    Vitova, Tonya

    2008-02-15

    The type and concentration of impurity centers in different valence states are crucial for tuning the photorefractive properties of doped Lithium Niobate (LN) crystals. X-ray Absorption Spectroscopy (XAS) is an appropriate tool for studying the local structure of impurity centers. XAS combined with absorption in UV/VIS/IR and High Resolution X-ray Emission Spectroscopy (HRXES) provide information about the valence state of the dopant ions in as-grown, reduced or oxidized doped LN crystals. Cu (Cu{sup 1+} and Cu{sup 2+}) and Fe (Fe{sup 2+} and Fe{sup 3+}) atoms are found in two different valence states, whereas there are indications for a third Mn valency, in addition to Mn{sup 2+} and Mn{sup 3+} in manganese-doped LN crystals. One of the charge compensation mechanisms during reduction of copper- doped LN crystals is outgassing of oxygen atoms. Cu ions in the reduced crystals have at least two different site symmetries: twofold (Cu{sup 1+}) and sixfold (Cu{sup 2+}) coordinated by O atoms. Fe and Mn atoms are coordinated by six O atoms. Cu and Fe ions are found to occupy only Li sites, whereas Mn ions are also incorporated into Li and Nb sites. The refractive index change in LN crystals irradiated with {sup 3}He{sup 2+} ions is caused by structurally disordered centers, where Nb atoms are displaced from normal crystallographic sites and Li or/and O vacancies are present. (orig.)

  9. Stark absorption spectroscopy of peridinin and allene-modified analogues

    Kusumoto, Toshiyuki; Horibe, Tomoko [Department of Physics and CREST-JST, Graduated School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); Kajikawa, Takayuki; Hasegawa, Shinji [Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Gakuen 2-1, Sanda, Hyogo 669-1337 (Japan); Iwashita, Takashi [Suntory Institute for Bioorganic Research, Wakayamadai 1-1-1, Shimamoto, Mishimagunn, Osaka 618-8503 (Japan); Cogdell, Richard J. [Glasgow Biomedical Research Centre, University of Glasgow, 120 University Place, Glasgow G12 8QQ, Scotland (United Kingdom); Birge, Robert R.; Frank, Harry A. [Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, CT 06269-3060 (United States); Katsumura, Shigeo [Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Gakuen 2-1, Sanda, Hyogo 669-1337 (Japan); Hashimoto, Hideki, E-mail: hassy@sci.osaka-cu.ac.jp [Department of Physics and CREST-JST, Graduated School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan)

    2010-07-19

    Stark absorption spectra of peridinin (Per) and five allene-modified analogues and their angular dependence as a function of an externally applied electric field were measured in methyl methacrylate polymer at 77 K. In all cases, the energetically lowest absorption band has a significant change of static dipole-moment upon photoexcitation ({Delta}{mu}). In particular, Per has the largest value of |{Delta}{mu}|. The angles between {Delta}{mu} and the transition dipole-moment of all the analogues were determined. It is suggested that the allene group in Per plays a key role as the electron donor in the charge transfer process following photoexcitation. The results of MNDO-PSDCI calculations support this idea.

  10. Mapping of the Local Interstellar Medium using Absorption Line Spectroscopy

    Penprase, Bryan Edward

    2017-01-01

    Using the Yale SMARTS 1.5-meter telescope at CTIO and the CHIRON spectrograph, we have developed a program for mapping the local interstellar medium using a sample of over 200 newly observed B stars previously unobserved using Na I absorption lines. This sample includes stars that extend out to map beyond the local bubble to 500 pc. The sample has been observed using high resolution absorption lines, and when combined with previously observed stars with Na I and Ca II data provides a more complete picture of the local ISM than previous surveys. The distances to the stars using the new GAIA database also allows for more accurate determination of distances to features in the lcoal ISM, and new maps of the structure of the ISM hav been prepared with the data.

  11. X-Ray Absorption Spectroscopy of Strontium(II) Coordination.

    O'Day; Newville; Neuhoff; Sahai; Carroll

    2000-02-15

    Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray absorption fine structure (EXAFS) were used to quantify local thermal and static disorder and to characterize strontium coordination in a variety of oxygen-ligated bonding environments. Analysis of anharmonic vibrational disorder (i.e., significant contribution from a third cumulant term (C(3)) in the EXAFS phase-shift function) in compounds with low and high static disorder around strontium showed that first-shell anharmonic contributions were generally not significant above experimental error in the EXAFS fits (R+/-0.02 Å with and without C(3)). The only case in which a significant apparent decrease in Sr-O distance was observed with increasing temperature, and for which a third cumulant term was significant, was for dilute strontium in aqueous solution. Empirical parameterization of Debye-Waller factor (sigma(2)) for strontium compounds as a function of backscatterer atomic number (Z), interatomic Sr-Z distance, and temperature of spectral data collection showed systematic increases in sigma(2) as a function of increasing temperature and Sr-Z bond length. At values of sigma(2) greater than approximately 0.025 Å(2) (for N3 Å), backscattering was generally not significant above noise levels in spectra of compounds of known crystal structure. Comparison of the EXAFS spectra of freshly precipitated SrCO(3) (spectra collected wet) to that of dry, powdered strontianite (SrCO(3)(s)) indicated no significant differences in the local atomic structure around strontium. Analysis of partially hydrated strontium in natural Ca-zeolite (heulandite) showed that strontium is substituted only in the calcium (Ca2) site. Backscattering from aluminum and silicon atoms in the zeolite framework were apparent in the EXAFS spectra at low and room temperature at distances from central strontium of strontium structural coordination determined

  12. Infrared absorption spectroscopy of CO 2-Ar complexes

    Sharpe, S. W.; Sheeks, R.; Wittig, C.; Beaudet, R. A.

    1988-10-01

    The ν 4 rovibrational band of CO 2-Ar near 2350 cm -1 (i.e. CO 2 asymmetric stretch) has been recorded in absorption at 8 K using a tunable diode laser. Rotational constants for both ν 4=0 and 1 are very similar, and indicate a T-shaped geometry. It was not possible to detect this species mass spectrometrically (18-70 eV electrons), indicating extensive fragmentation.

  13. Molecular characterization of brominated persistent pollutants using extended X-ray absorption fine structure (EXAFS) spectroscopy

    Bergknut, Magnus; Skyllberg, Ulf [Swedish University of Agricultural Sciences (SLU), Department of Forest Ecology and Management, Umeaa (Sweden); Persson, Per [Umeaa University, Department of Chemistry, Umeaa (Sweden)

    2008-02-15

    X-ray absorption fine structure (EXAFS) spectroscopy spectra were collected for three brominated persistent pollutants: 6-bromo-2,4,5-trichlorophenol (BrTriClP), pentabromophenol (PentaBrP) and 3,3',5,5'-tetrabromobisphenol A (TBBA). The substances were selected to be symmetrical (BrTriClP and TBBA) or asymmetrical (PentaBrP) with respect to the atomic Br positions and to differ in the number of bromine and other halide atoms, as well as their relative positions. The asymmetrical PentaBrP was modelled with special detail as not all bromine atoms have identical coordination environments. The studied substances displayed unique EXAFS spectra, which could be used to determine the molecular structure in fair detail. We conclude that EXAFS spectroscopy is a suitable technique for molecular characterization of the comparatively complex molecules within the class of compounds of brominated organic persistent pollutants. A detailed understanding of the EXAFS spectra of the pure compounds opens up possibilities to study the interactions with soil and sediment matrices by means of EXAFS spectroscopy. (orig.)

  14. Coordination nature of aluminum (oxy)hydroxides formed under the influence of low molecular weight organic acids and a soil humic acid studied by X-ray absorption spectroscopy

    Xu, R. K.; Hu, Y. F.; Dynes, J. J.; Zhao, A. Z.; Blyth, R. I. R.; Kozak, L. M.; Huang, P. M.

    2010-11-01

    Organic ligands in the environment hinder the formation of crystalline Al precipitation products by perturbing the hydrolytic and polymeric reactions of Al resulting in the formation of short-range ordered (SRO) mineral colloids with varying degrees of crystallinity. However, the effect of these ligands on the mechanisms of their formation and nature of the transformation products of Al (oxy)hydroxides at the atomic and molecular levels is not well understood. In this study, the coordination structure of Al in Al (oxy)hydroxides formed under the influence of varying concentrations of low molecular weight (LMW) organic acids such as citric, malic, salicylic and acetic acids and a humic acid (HA) was investigated with X-ray absorption near edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis. The Al K- and L-edge XANES spectra showed that with increasing LMW organic acid concentration the coordination number of Al changed from 6-fold to a mixture of 4- and 6-fold, except for acetate as acetate was unable to perturb the formation of Al (oxy)hydroxides at the acetate/Al molar ratio (MR) = 0.1. The proportion of 4-fold to 6-fold coordinated Al in the Al precipitation products depended on the structure and functionality of the LMW organic acids. The incorporation of the LMW organic acid into the network structure of Al (oxy)hydroxides prevented the formation of sheets/inter-layer H-bonding that was required for the formation of crystalline Al (oxy)hydroxides. The HA used in this study only slightly perturbed the crystallization of the Al (oxy)hydroxides at the concentrations used. The Al K-edge data showed that Al coordination number had not been altered in the presence of HA. The findings obtained in the present study are of fundamental significance in understanding the physicochemical behavior of soils and sediments, and their relation to the accumulation and transport of nutrients and pollutants in the

  15. Measurements of Iodine Monoxide Levels During the CAST Campaign Using Broadband Cavity Enhanced Absorption Spectroscopy

    Harris, N. R. P.; Popoola, O. A.; McLeod, M.; Ouyang, B.; Jones, R. L.

    2014-12-01

    Iodine monoxide (IO) has been regarded as an important radical involved in the ozone destruction in the remote marine boundary layer. Here we presented the first in situ aircraft measurements of IO using broadband cavity enhanced absorption spectroscopy with 1s -sensitivity of ~1.5 ppt Hz-1/2 on the surface level during the Coordinated Airborne Studies in the Tropics (CAST) campaign between January - February 2014. IO was retrieved from analysis of absorption spectrum recorded between 415 nm - 452.5 nm. Instrument baseline corresponding to the "zero" signal of IO was obtained by injection of ~20 ppb of nitric oxide (NO) into the sample air at chosen frequency and period. No clear absorption feature was observable from the spectra by eye with up to 100 seconds averaging, pointing to very low mixing ratios (<~0.5 ppt) of IO over the sampled area. A small positive bias (~0.3 ppt) of IO (against the baseline signal during NO titration) was obtained in the statistical histogram of retrieved IO from average of each straight and level run, but little altitude dependence was noted. In summary, our observation appears to support the existence of IO in the remote marine boundary above the Pacific Ocean at sub ppt levels, but the limited sensitivity precludes us from quantifying spatial gradients more accurately.

  16. Sedimentation field flow fractionation and optical absorption spectroscopy for a quantitative size characterization of silver nanoparticles.

    Contado, Catia; Argazzi, Roberto; Amendola, Vincenzo

    2016-11-04

    Many advanced industrial and biomedical applications that use silver nanoparticles (AgNPs), require that particles are not only nano-sized, but also well dispersed, not aggregated and not agglomerated. This study presents two methods able to give rapidly sizes of monodispersed AgNPs suspensions in the dimensional range of 20-100nm. The first method, based on the application of Mie's theory, determines the particle sizes from the values of the surface plasmon resonance wavelength (SPRMAX), read from the optical absorption spectra, recorded between 190nm and 800nm. The computed sizes were compared with those determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) and resulted in agreement with the nominal values in a range between 13% (for 20nm NPs) and 1% (for 100nm NPs), The second method is based on the masterly combination of the Sedimentation Field Flow Fractionation (SdFFF - now sold as Centrifugal FFF-CFFF) and the Optical Absorption Spectroscopy (OAS) techniques to accomplish sizes and quantitative particle size distributions for monodispersed, non-aggregated AgNPs suspensions. The SdFFF separation abilities, well exploited to size NPs, greatly benefits from the application of Mie's theory to the UV-vis signal elaboration, producing quantitative mass-based particle size distributions, from which trusted number-sized particle size distributions can be derived. The silver mass distributions were verified and supported by detecting off-line the Ag concentration with the graphite furnace atomic absorption spectrometry (GF-AAS).

  17. Insight into the structure of Pd/ZrO2 during the total oxidation of methane using combined in situ XRD, X.-ray absorption and Raman spectroscopy

    Grunwaldt, Jan-Dierk; van Vegten, Niels; Baiker, Alfons;

    2009-01-01

    The structure of palladium during the total combustion of methane has been studied by a combination of the complementary in situ techniques X-ray absorption spectroscopy, Raman spectroscopy and X-ray diffraction. The study demonstrates that finely dispersed and oxidized palladium is most active f...

  18. Non-coincident multi-wavelength emission absorption spectroscopy

    Baumann, L.E.

    1995-02-01

    An analysis is presented of the effect of noncoincident sampling on the measurement of atomic number density and temperature by multiwavelength emission absorption. The assumption is made that the two signals, emission and transmitted lamp, are time resolved but not coincident. The analysis demonstrates the validity of averages of such measurements despite fluctuations in temperature and optical depth. At potassium-seeded MHD conditions, the fluctuations introduce additional uncertainty into measurements of potassium atom number density and temperature but do not significantly bias the average results. Experimental measurements in the CFFF aerodynamic duct with coincident and noncoincident sampling support the analysis.

  19. A GAS TEMPERATURE PROFILE BY INFRARED EMISSION-ABSORPTION SPECTROSCOPY

    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

  20. The Application of Atomic Absorption Spectroscopy and Optical Microscopy to the Characterization of Sized Airborne Particulate in Dayton, Ohio.

    1978-01-01

    PERIOD COVERED " AneT Appication of Atomic Absorption Spectroscopy ’ and Optical Microscopy to the Characterization of THESIS/DISSERTATION 4 Sized...1978 U I HEREBY REC04MEND THAT THE THESIS PREPARED ’NDER MY SUPERVISION BY Lorelei Ann Krebs ENTITLED The Application of Atomic Absorption Spectroscopy and...acid and diluted with distilled water in a 25 milliliter volumetric flask. Atomic absorption . spectroscopy was used to analyze the solutions for

  1. Fourier transform infrared absorption spectroscopy of jet-cooled radicals

    Rohrs, Henry W.; Wickham-Jones, C. Tom; Ellison, G. Barney; Berry, David; Argrow, Brian M.

    1995-03-01

    We describe an experiment that couples a high-resolution Fourier transform spectrometer (FTS) to a supersonic jet of radicals. A 1-mm-i.d. cylindrical SiC nozzle is resistively heated to 1500 K in order to decompose organic precursors and generate expansions of jet-cooled radicals. We have used this apparatus to pyrolyze alkyl nitrites to make alkoxy and nitric oxide radicals. The residence time of radicals in this hot nozzle is roughly 20 μs RONO→ΔRO+NO. We use the FTS to detect the IR absorption of the product NO (ν0=1876.1 cm-1) at resolutions as fine as 0.005 cm-1 FWHM. We observe the product NO from the pyrolysis of CH3CH2ONO to be rotationally cooled to roughly 50 K. The IR spectra indicate that the optical path length is about 3/4 cm and that the nitrites pyrolyze to produce approximately 1014 NO radicals cm-3 some 9 mm downstream from the nozzle. Our spectrometer is capable of detecting an absorption signal of 0.1% over a bandwidth of 100 cm-1 at 0.005 cm-1 resolution. Depending on the infrared cross section of the radical, this implies that we are able to monitor diatomic radical densities of roughly 5×1012 cm-3 (quantum state)-1.

  2. Mechanistic Study of CO 2 Photoreduction with H 2 O on Cu/TiO 2 Nanocomposites by in Situ X-ray Absorption and Infrared Spectroscopies

    Liu, Lianjun; Zhao, Cunyu; Miller, Jeffrey T.; Li, Ying

    2016-12-15

    Cu/TiO2 composites are extensively studied for photocatalytic reduction of CO2 with H2O, but the roles of Cu species (Cu2+, Cu+, or Cu0) is not well understood, and the photocatalyst deactivation mechanism is seldom addressed. In this work, we have employed in situ techniques, i.e., X-ray absorption spectroscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), to explore the surface chemistry of Cu/TiO2 composites under CO2 photoreduction environment. We found that the air-calcined Cu/TiO2 (Cu/Ti(air)) surface was dominated by isolated Cu2+ sites, while the one post-treated with H2 at 200 °C (Cu/Ti(H2)) was rich in Cu+ and oxygen vacancy (VO). Cu/Ti(H2) showed more than 50% higher activity than Cu/Ti(air) for CO2 photoreduction to CO, mainly resulting from the synergy of Cu+, OH groups, and VO that could scavenge holes to enhance electron transfer, provide CO2 adsorption sites, and facilitate the activation and conversion of the adsorbed CO2 (HCO3– and CO2–). Meanwhile, the consumption of OH groups and Cu+ active sites by holes may result in the deactivation of Cu/Ti(H2). Moreover, in situ XAS results directly demonstrated that (1) the photoinduced oxidation of Cu+ to Cu2+ changed the surrounding environments of Cu by increasing the coordination number; (2) thermal treatment by H2 could not fully recover the OH and Cu+ sites to their original states; and (3) adding hole scavengers (e.g., methanol) maintained or even increased the more active Cu+ species from the photoreduction of Cu2+, thus leading to a higher and more stable CO2 reduction activity. Findings in this work and the application of in situ XAS technique will help develop a more efficient photocatalyst for CO2 photoreduction and advance the understanding of the reaction mechanism and surface chemistry.

  3. Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

    Cahill, A. D., E-mail: adc87@cornell.edu; Hoyt, C. L., E-mail: adc87@cornell.edu; Shelkovenko, T. A., E-mail: adc87@cornell.edu; Pikuz, S. A., E-mail: adc87@cornell.edu; Hammer, D. A., E-mail: adc87@cornell.edu [Cornell University, 439 Rhodes Hall, Ithaca, NY 14853 (United States)

    2014-12-15

    X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emitted by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here initial absorption spectra obtained from an aluminum x-pinch plasma.

  4. Quasi zero-background tunable diode laser absorption spectroscopy employing a balanced Michelson interferometer.

    Guan, Zuguang; Lewander, Märta; Svanberg, Sune

    2008-12-22

    Tunable diode laser spectroscopy (TDLS) normally observes small fractional absorptive reductions in the light flux. We show, that instead a signal increase on a zero background can be obtained. A Michelson interferometer, which is initially balanced out in destructive interference, is perturbed by gas absorption in one of its arms. Both theoretical analysis and experimental demonstration show that the proposed zero-background TDLS can improve the achievable signal-to-noise ratio.

  5. Absorption-Line Studies of Seyfert Galaxies

    Shull, J. Michael

    We propose to undertake a "reverberation analysis" of the variable absorption lines ill two Seyfert Galaxies (NGC 4051 and Mrk 279) to help understand the origin of intrinsic absorption lines in AGNs. Stich an analysis is a powerful tool for elucidating the radial distribution of absorbing gas in the broad-line region (BLR) and narrow-line region (NLR). Only two Seyferts have previously been studied with this technique: NGC 4151 (Bromage el al. 1985; Clavel et al. 1987) and NGC 3516 (Voit, Shull, and Begelman 1987). The absorption features have been interpreted as an outflow of ionized clouds from the nuclear region or from an accretion disk affected by UV/X-ray heating. Neither the source of the absorbing gas in these Seyferts nor the "gene" which distingishes them from other Seyferts is known. Until the 1984 onset of absorption in Mrk 279, broad self-absorbed. lines had been observed only in Seyferts of low intrinsic luminosity, such as NGC 4051. Mrk 279 is intrinsically much brighter, and therefore more quasar-like, than the other three absorptionline Seyfert I's in the CfA sample. Thus, it may show how the absorption phenomenon changes at higher luminosity and could bridge the gap between the low luminosity absorption-line Seyferts and the well-studied broad absorption-line (BAL) QSO's. In addition, Mrk 279's significant redshift will allow us to study, for the first time, the Ly-alpha line in an absorption-line Seyfert. With 3 US-1 shifts for each of these two underobserved Seyferts, we can double the number of objects in which absorption-line variability has been studied and investigate why the absorption-line strengths correlate or anti-correlate with the UV continuum.

  6. INTEGRAL FIELD SPECTROSCOPY OF AGN ABSORPTION OUTFLOWS: MRK 509 AND IRAS F04250–5718

    Liu, Guilin; Arav, Nahum [Department of Physics, Virginia Tech, Blacksburg, VA 24061 (United States); Rupke, David S. N., E-mail: glliu@vt.edu [Department of Physics, Rhodes College, Memphis, TN 38112 (United States)

    2015-11-15

    Ultraviolet (UV) absorption lines provide abundant spectroscopic information enabling the probe of the physical conditions in active galactic nucleus (AGN) outflows, but the outflow radii (and the energetics consequently) can only be determined indirectly. We present the first direct test of these determinations using integral field unit (IFU) spectroscopy. We have conducted Gemini IFU mapping of the ionized gas nebulae surrounding two AGNs, whose outflow radii have been constrained by UV absorption line analyses. In Mrk 509, we find a quasi-spherical outflow with a radius of 1.2 kpc and a velocity of ∼290 km s{sup −1}, while IRAS F04250–5718 is driving a biconical outflow extending out to 2.9 kpc, with a velocity of ∼580 km s{sup −1} and an opening angle of ∼70°. The derived mass flow rate ∼5 and >1 M{sub ⊙} yr{sup −1}, respectively, and the kinetic luminosity ≳1 × 10{sup 41} erg s{sup −1} for both. Adopting the outflow radii and geometric parameters measured from IFU, absorption line analyses would yield mass flow rates and kinetic luminosities in agreement with the above results within a factor of ∼2. We conclude that the spatial locations, kinematics, and energetics revealed by this IFU emission-line study are consistent with pre-existing UV absorption line analyses, providing a long-awaited direct confirmation of the latter as an effective approach for characterizing outflow properties.

  7. Understanding the collapse mechanism in Langmuir monolayers through polarization modulation-infrared reflection absorption spectroscopy.

    Goto, Thiago Eichi; Caseli, Luciano

    2013-07-23

    The collapse of films at the air-water interface is related to a type of 2D-to-3D transition that occurs when a Langmuir monolayer is compressed beyond its stability limit. Studies on this issue are extremely important because defects in ultrathin solid films can be better understood if the molecular mechanisms related to collapse processes are elucidated. This paper explores how the changes of vibration of specific groups of lipid molecules, as revealed by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS), are affected by the monolayer collapse. Different mechanisms of collapse were studied, for those lipids that undergo constant-area collapse (such as stearic acid) and for those that undergo constant-pressure collapse (such as DPPC, DPPG, and DODAB). Lipid charges also affect the mechanism of collapse, as demonstrated for two oppositely charged lipids.

  8. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states.

  9. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    Yifan Ye

    2016-01-01

    Full Text Available The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH215N+(CH33Br− and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.

  10. The effect of hydrogen absorption on the structural, electronic and magnetic properties of the C15 Friauf-Laves phase compounds CeFe{sub 2}, CeRu{sub 2} and LaRu{sub 2} : an x-ray absorption spectroscopy (XAS) study

    Chaboy, J.; Garcia, J. [CSIC-Univ., Zaragoza (Spain). Inst. de Ciencia de Materiales de Aragon ICMA; Marcelli, A. [INFN, Laboratori Nazionali di Frascati, Rome (Italy)

    1995-08-01

    An x-ray absorption spectroscopy (XAS) investigation of the structural changes occurred upon hydriding in the Friauf-Laves phase compounds CeFe{sub 2}, CeRu{sub 2}and LaRu{sub 2} compounds is presented. The analysis of the extended x-ray absorption spectroscopy (EXAFS) spectra at the L-edges of the rare-earth and at the Fe K-edge indicates that the hydrogenation process leads to the suppression of the long-range crystalline order in all the hydride derivates investigated, as well as the different influence of H{sub 2} in both the rare earth and transition metal sublattices. The correlation between the structural and magnetic changes induced by the hydrogen in the lost matrix is discussed in terms of the modification of the electronic properties, i.e., intermediate-valence of Ce, and of the hybridization between the transition metal and rare-earth.

  11. Time-Resolved Broadband Cavity-Enhanced Absorption Spectroscopy behind Shock Waves.

    Matsugi, Akira; Shiina, Hiroumi; Oguchi, Tatsuo; Takahashi, Kazuo

    2016-04-07

    A fast and sensitive broadband absorption technique for measurements of high-temperature chemical kinetics and spectroscopy has been developed by applying broadband cavity-enhanced absorption spectroscopy (BBCEAS) in a shock tube. The developed method has effective absorption path lengths of 60-200 cm, or cavity enhancement factors of 12-40, over a wavelength range of 280-420 nm, and is capable of simultaneously recording absorption time profiles over an ∼32 nm spectral bandpass in a single experiment with temporal and spectral resolutions of 5 μs and 2 nm, respectively. The accuracy of the kinetic and spectroscopic measurements was examined by investigating high-temperature reactions and absorption spectra of formaldehyde behind reflected shock waves using 1,3,5-trioxane as a precursor. The rate constants obtained for the thermal decomposition reactions of 1,3,5-trioxane (to three formaldehyde molecules) and formaldehyde (to HCO + H) agreed well with the literature data. High-temperature absorption cross sections of formaldehyde between 280 and 410 nm have been determined at the post-reflected-shock temperatures of 955, 1265, and 1708 K. The results demonstrate the applicability of the BBCEAS technique to time- and wavelength-resolved sensitive absorption measurements at high temperatures.

  12. FeS-Quantum-Dot Sensitized Metal Oxide Photoelectrodes: Photoelectrochemistry and Photoinduced Absorption Spectroscopy

    Idriss Bedja

    2011-01-01

    Full Text Available TiO2, ZnO nanoparticulate(-np, and ZnO-nanorod(-nr electrodes have been modified with FeS2 (pyrite nanoparticles. Quantum size effect is manifested by a blue shift in both absorption and photocurrent action spectra. PIA (photoinduced absorption spectroscopy, a multipurpose tool in the study of dye-sensitized solar cells, is used to study quantum-dot modified metal oxide (MO nanostructured electrodes. The PIA spectra showed an evidence for long-lived photoinduced charge separation. Time-resolved PIA showed that recombination between electrons and holes occurs on a millisecond timescale. Incident-photon-to-current efficiencies at 400 nm are ranged between 13% and 25%. The better solar cell performance of FeS2 on ZnO-nr over ZnO-np can be ascribed to the faster, unidirectional e-transport channels through the ZnO-nr as well as the longer electron lifetimes. The lower performances of electrodes can be explained by the presence of FeS2 phases other than the photoactive pyrite phase, as evidenced from XRD study.

  13. Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy.

    Wizemann, H D

    2000-01-01

    Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer.

  14. Spectroscopy of PTCDA attached to rare gas samples: clusters vs. bulk matrices. I. Absorption spectroscopy

    Dvorak, M; Knoblauch, T; Bünermann, O; Rydlo, A; Minniberger, S; Harbich, W; Stienkemeier, F

    2012-01-01

    The interaction between PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) and rare gas or para-hydrogen samples is studied by means of laser-induced fluorescence excitation spectroscopy. The comparison between spectra of PTCDA embedded in a neon matrix and spectra attached to large neon clusters shows that these large organic molecules reside on the surface of the clusters when doped by the pick-up technique. PTCDA molecules can adopt different conformations when attached to argon, neon and para-hydrogen clusters which implies that the surface of such clusters has a well-defined structure and has not liquid or fluxional properties. Moreover, a precise analysis of the doping process of these clusters reveals that the mobility of large molecules on the cluster surface is quenched, preventing agglomeration and complex formation.

  15. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-09-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms.

  16. Determination of palladium by graphite furnace atomic absorption spectroscopy without matrix matching.

    Jia, X; Wang, T; Wu, J

    2001-05-30

    A graphite furnace atomic absorption spectroscopy method for the analysis of the palladium (Pd) content in bulk pharmaceutical drug substances and their intermediates prepared in aqueous solutions is extended to samples prepared in acetonitrile (ACN) and ACN-water mixtures as well to samples prepared in dimethyl sulfoxide (DMSO) and DMSO-water mixtures. The Pd content in samples solubilized in these solvents can be accurately determined with calibration established with standards prepared in aqueous solutions without matrix matching or using the method of standard additions. The validity of this method is demonstrated by spike recovery studies and by the agreement with results for the same samples prepared in these solvents, in concentrated nitric acid, and prepared by a microwave digestion system.

  17. Application of atomic absorption spectroscopy for detection of multimetal traces in low-voltage electrical marks.

    Jakubeniene, Marija; Zakaras, Algirdas; Minkuviene, Zita Nijole; Benoshys, Alvydas

    2006-08-10

    Application of atomic absorption spectroscopy to detect multimetal traces in injured skin is a promising tool for investigation of fatalities caused by electrocution. The present paper is aimed at testing the reliability of this method for metal traces detection in electric current marks and is focused on study of peculiarities of metal penetration into the skin exposed to a current impact. Bare aluminum wire, tin-lead coated copper multistrand wire, and zinc-plated steel rope were used to make electrical marks on pig skin. It is demonstrated that amount of copper, zinc, lead, and iron may serve as statistically reliable indicators for the type of wire, which caused the electrical mark, in spite of the background content of these metals in the skin without injury. Different penetration rates for different metals contained in the wire inflicting an electrical mark were observed.

  18. Excited state absorption spectroscopy of ZBLAN:Ho{sup 3+} glass-experiment and simulation

    Piatkowski, D; Wisniewski, K; Rozanski, M; Koepke, Cz [Institute of Physics, Nicolaus Copernicus University, Grudziadzka 5/7, 87-100 Torun (Poland); Kaczkan, M; Klimczak, M; Piramidowicz, R; Malinowski, M [Institute of Microelectronics and Optoelectronics, Koszykowa 75, 00-662 Warsaw (Poland)], E-mail: dapi@fizyka.umk.pl

    2008-04-16

    The excited state absorption (ESA) spectra of ZBLAN glass activated by trivalent holmium ions have been measured in a wide spectral range (550-1750 nm) and simulated using such theoretical tools as the Judd-Ofelt formalism and McCumber theory of stimulated emission. We also propose a systematic approach for prediction of various types of up-conversion mechanisms in a given type of material. Experimental results on ESA up-conversion processes in ZBLAN:Ho{sup 3+} under red and infrared laser excitation, which confirm theoretical analysis, are presented. The optical linewidths were studied using high resolution laser spectroscopy at low temperatures and the existence of different crystallographic sites for Ho{sup 3+} ions was revealed.

  19. Excited state absorption spectroscopy of ZBLAN:Ho3+ glass—experiment and simulation

    Piatkowski, D.; Wisniewski, K.; Rozanski, M.; Koepke, Cz; Kaczkan, M.; Klimczak, M.; Piramidowicz, R.; Malinowski, M.

    2008-04-01

    The excited state absorption (ESA) spectra of ZBLAN glass activated by trivalent holmium ions have been measured in a wide spectral range (550-1750 nm) and simulated using such theoretical tools as the Judd-Ofelt formalism and McCumber theory of stimulated emission. We also propose a systematic approach for prediction of various types of up-conversion mechanisms in a given type of material. Experimental results on ESA up-conversion processes in ZBLAN:Ho3+ under red and infrared laser excitation, which confirm theoretical analysis, are presented. The optical linewidths were studied using high resolution laser spectroscopy at low temperatures and the existence of different crystallographic sites for Ho3+ ions was revealed.

  20. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

    Curl, Robert F.; Glass, Graham P.

    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.

  1. Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

    Karhu, J; Vainio, M; Metsälä, M; Hoekstra, S; Halonen, L

    2016-01-01

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, $\

  2. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-01-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms. PMID:27658854

  3. The Optical Absorption Coefficient of Maize Grains Investigated by Photoacoustic Spectroscopy

    Rodríguez-Páez, C. L.; Carballo-Carballo, A.; Rico-Molina, R.; Hernández-Aguilar, C.; Domínguez-Pacheco, A.; Cruz-Orea, A.; Moreno-Martínez, E.

    2017-01-01

    In the maize and tortilla industry, it is important to characterize the color of maize ( Zea mays L.) grain, as it is one of the attributes that directly affect the quality of the tortillas consumed by the population. For this reason, the availability of alternative techniques for assessing and improving the quality of grain is valued. Photoacoustic spectroscopy has proven to be a useful tool for characterizing maize grain. So, the objective of the present study was to determine the optical absorption coefficient β of the maize grain used to make tortillas from two regions of Mexico: (a) Valles Altos, 2012-2013 production cycle and (b) Guasave, Sinaloa, 2013-2014 production cycle. Traditional reflectance measurements, physical characteristics of the grain and nutrient content were also calculated. The experimental results show different characteristics for maize grains.

  4. Quantitation of a novel metalloporphyrin drug in plasma by atomic absorption spectroscopy.

    Hoffman, K L; Feng, M R; Rossi, D T

    1999-03-01

    A bioanalytical method to quantify cobalt mesoporphyrin (CoMP), a novel therapeutic agent, in plasma has been developed and validated. The approach involves atomic absorption spectroscopy to determine total cobalt in a sample and a back-calculation of the amount of compound present. Endogenous plasma cobalt concentrations were small ( <0.2 ng/ml(-1) Co in rat plasma) in comparison to the quantitation limit (4.5 ng/ml(-1) Co). The inter-day imprecision of the method was 10.0% relative standard deviation (RSD) and the inter-day bias was +/- 8.0% relative error (RE) over a standard curve range of 4.5- 45.0 ng/ml(-1) Co. Because it quantifies total cobalt, the method cannot differentiate between parent drug and metabolites, but negligible metabolism allows reliable estimates of the actual parent drug concentration. A correlation study between the atomic absorption method and 14C-radiometry demonstrated excellent agreement (r = 0.9868, slope = 1.041 +/- 0.028, intercept = 223.7 +/- 190.0) and further substantiated the accuracy of the methods. Methodology was successfully applied to a pharmacokinetic study of CoMP in rat, with pharmacokinetic parameter estimation. The elimination half-lives, after intra-muscular and subcutaneous administration, were 7.7 and 8.8 days, respectively.

  5. Vacuum-UV absorption spectroscopy of interstellar ice analogues. III. Isotopic effects

    Cruz-Diaz, G A; Chen, Y -J

    2014-01-01

    This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave discharged hydrogen flow lamp as the VUV source. Prior to this work, we have recently submitted a similar study of the light isotopologues (Cruz-Diaz, Mu\\~noz Caro and Chen). The VUV spectra are compared to those of the light isotopologues in the solid phase, and to the gas phase spectra of the same molecules. Our study is expected to improve very significantly the models that estimate the VUV absorption of ice mantles in space, which hav...

  6. Photo-induced dynamics in heterocyclic aromatic molecules probed by femtosecond XUV transient absorption spectroscopy

    Lackner, Florian; Chatterley, Adam S.; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.; Gessner, Oliver

    2016-05-01

    We report on the ring-opening and dissociation dynamics of strong-field ionized selenophene (C4 H4 Se), studied by transient XUV absorption spectroscopy at the Se 3d edge. The table-top experiments are facilitated by high-order harmonic generation coupled with a gas phase transient XUV absorption setup that is optimized for the study of organic compounds. Employing element-specific core-to-valence transitions, the ultrafast molecular dynamics are monitored from the perspective of the well-localized Se atoms. Spectral features are assigned based on first principles TDDFT calculations for a large manifold of electronic states. We observe signatures of rapidly (~ 35 fs) decaying highly excited molecular cations, the formation of ring-opened products on a 100 fs time scale and, most notably, the elimination of bare Se+ ions in a very rapid multi-step process. A delayed onset of the Se+ ions provides direct evidence that both selenium-carbon bonds are broken within only ~ 130 fs and that a sequential mechanism, presumably an initial ring-opening followed by a subsequent breaking of the second bond, is required to eliminate the atomic fragments.

  7. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy.

    Chen, Li; Ueta, Hirokazu; Bisson, Régis; Beck, Rainer D

    2013-05-01

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S(θ). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  8. DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

    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...

  9. Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

    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.

  10. Electro-Optical Multichannel Spectrometer for Transient Resonance Raman and Absorption Spectroscopy

    Hansen, Karina Benthin; Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn

    1979-01-01

    An optical multichannel system is described, used for time‐dependent absorption measurements in the gas phase and the liquid phase and for resonance Raman spectroscopy of short‐lived transient species in the liquid phase in pulse radiolysis. It consists of either an image converter streak unit or...

  11. Cationic Tri-Rhenium Rafts on gamma-Alumina: Characterization by X-ray Absorption Spectroscopy

    Koningsberger, D.C.; Fung, A.S.; Tooley, P.A.; Kelley, M.J.; Gates, B.C.

    1991-01-01

    Rhenium surface species, derived by treating [H,Re,(CO),,] adsorbed on y-A1203 in hydrogen at 400 'C, formed extremely small surface grouping of rhenium atoms having an average Re-Re coordination number of 2, as determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. Results of

  12. Absorption spectroscopy of glucose based on a silicon photonics evanescent sensor

    2013-01-01

    We present a silicon photonics evanescent sensor for glucose absorption spectroscopy. The important design aspects of this miniature sensor are discussed as well as the experimental challenges. We demonstrate detection of glucose down to 14 mmol/L, close to the physiological range of blood glucose in humans.

  13. Synchrotron radiation based Mössbauer absorption spectroscopy of various nuclides

    Masuda, Ryo; Kobayashi, Yasuhiro; Kitao, Shinji; Kurokuzu, Masayuki; Saito, Makina; Yoda, Yoshitaka; Mitsui, Takaya; Seto, Makoto

    2016-12-01

    Synchrotron-radiation (SR) based Mössbauer absorption spectroscopy of various nuclides is reviewed. The details of the measuring system and analysis method are described. Especially, the following two advantages of the current system are described: the detection of internal conversion electrons and the close distance between the energy standard scatterer and the detector. Both of these advantages yield the enhancement of the counting rate and reduction of the measuring time. Furthermore, SR-based Mössbauer absorption spectroscopy of 40K, 151Eu, and 174Yb is introduced to show the wide applicability of this method. In addition to these three nuclides, SR-based Mössbauer absorption spectroscopy of 61Ni, 73Ge, 119Sn, 125Te, 127I, 149Sm, and 189Os has been performed. We continue to develop the method to increase available nuclides and to increase its ease of use. The complementary relation between the time-domain method using SR, such as nuclear forward scattering and the energy-domain methods such as SR-based Mössbauer absorption spectroscopy is also noted.

  14. Characterising legacy spent nuclear fuel pond materials using microfocus X-ray absorption spectroscopy.

    Bower, W R; Morris, K; Mosselmans, J F W; Thompson, O R; Banford, A W; Law, K; Pattrick, R A D

    2016-11-05

    Analysis of a radioactive, coated concrete core from the decommissioned, spent nuclear fuel cooling pond at the Hunterston-A nuclear site (UK) has provided a unique opportunity to study radionuclides within a real-world system. The core, obtained from a dividing wall and sampled at the fill level of the pond, exhibited radioactivity (dominantly (137)Cs and (90)Sr) heterogeneously distributed across both painted faces. Chemical analysis of the core was undertaken using microfocus spectroscopy at Diamond Light Source, UK. Mapping of Sr across the surface coatings using microfocus X-ray fluorescence (μXRF) combined with X-ray absorption spectroscopy showed that Sr was bound to TiO2 particles in the paint layers, suggesting an association between TiO2 and radiostrontium. Stable Sr and Cs sorption experiments using concrete coupons were also undertaken to assess their interactions with the bulk concrete in case of a breach in the coating layers. μXRF and scanning electron microscopy showed that Sr was immobilized by the cement phases, whilst at the elevated experimental concentrations, Cs was associated with clay minerals in the aggregates. This study provides a crucial insight into poorly understood infrastructural contamination in complex systems and is directly applicable to the UK's nuclear decommissioning efforts.

  15. X-ray Absorption Spectroscopy Characterization of Electrochemical Processes in Renewable Energy Storage and Conversion Devices

    Farmand, Maryam [George Washington Univ., Washington, DC (United States)

    2013-05-19

    The development of better energy conversion and storage devices, such as fuel cells and batteries, is crucial for reduction of our global carbon footprint and improving the quality of the air we breathe. However, both of these technologies face important challenges. The development of lower cost and better electrode materials, which are more durable and allow more control over the electrochemical reactions occurring at the electrode/electrolyte interface, is perhaps most important for meeting these challenges. Hence, full characterization of the electrochemical processes that occur at the electrodes is vital for intelligent design of more energy efficient electrodes. X-ray absorption spectroscopy (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.

  16. High-resolution absorption spectroscopy of the OH 2Pi 3/2 ground state line

    Wiesemeyer, Helmut; Heyminck, Stefan; Karl, Jacobs; Menten, Karl; Neufeld, David; Requena-Torres, Miguel Angel; Stutzki, Jürgen; 10.1051/0004-6361/201218915

    2012-01-01

    The chemical composition of the interstellar medium is determined by gas phase chemistry, assisted by grain surface reactions, and by shock chemistry. The aim of this study is to measure the abundance of the hydroxyl radical (OH) in diffuse spiral arm clouds as a contribution to our understanding of the underlying network of chemical reactions. Owing to their high critical density, the ground states of light hydrides provide a tool to directly estimate column densities by means of absorption spectroscopy against bright background sources. We observed onboard the SOFIA observatory the 2Pi3/2, J = 5/2 3/2 2.5 THz line of ground-state OH in the diffuse clouds of the Carina-Sagittarius spiral arm. OH column densities in the spiral arm clouds along the sightlines to W49N, W51 and G34.26+0.15 were found to be of the order of 10^14 cm^-2, which corresponds to a fractional abundance of 10^-7 to 10^-8, which is comparable to that of H_2O. The absorption spectra of both species have similar velocity components, and the...

  17. X-ray Absorption Spectroscopy of the Multi-phase Interstellar Medium: Oxygen and Neon Abundances

    Yao, Y; Yao, Yangsen

    2006-01-01

    X-ray absorption spectroscopy provides a potentially powerful tool in determining the metal abundances in various phases of the interstellar medium (ISM). We present a case study of the sight line toward 4U 1820-303 (Galactic coordinates l, b=2.79, -7.91 and distance = 7.6 kpc), based on Chandra Grating observations. The detection of OI, OII, OIII, OVII, OVIII, and NeIX Kalpha absorption lines allows us to measure the atomic column densities of the neutral, warm ionized, and hot phases of the ISM through much of the Galactic disk. By comparing these measurements with the 21 cm hydrogen emission and with the pulsar dispersion measure along the same sight line, we estimate the mean oxygen abundances in the neutral and total ionized phases as 0.3(0.2, 0.6) and 2.2(1.1, 3.5) in units of Anders & Grevesse (1989) solar value. This significant oxygen abundance difference is apparently a result of molecule/dust grain destruction and recent metal enrichment in the warm ionized and hot phases. We also measure the c...

  18. Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

    Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

    2017-01-01

    Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

  19. Calculation of the spatial resolution in two-photon absorption spectroscopy applied to plasma diagnosis

    Garcia-Lechuga, M. [Departamento de Física Teórica, Atómica y Óptica, Universidad de Valladolid, 47011-Valladolid (Spain); Laser Processing Group, Instituto de Óptica “Daza de Valdés,” CSIC, 28006-Madrid (Spain); Fuentes, L. M. [Departamento de Física Aplicada, Universidad de Valladolid, 47011-Valladolid (Spain); Grützmacher, K.; Pérez, C., E-mail: concha@opt.uva.es; Rosa, M. I. de la [Departamento de Física Teórica, Atómica y Óptica, Universidad de Valladolid, 47011-Valladolid (Spain)

    2014-10-07

    We report a detailed characterization of the spatial resolution provided by two-photon absorption spectroscopy suited for plasma diagnosis via the 1S-2S transition of atomic hydrogen for optogalvanic detection and laser induced fluorescence (LIF). A precise knowledge of the spatial resolution is crucial for a correct interpretation of measurements, if the plasma parameters to be analysed undergo strong spatial variations. The present study is based on a novel approach which provides a reliable and realistic determination of the spatial resolution. Measured irradiance distribution of laser beam waists in the overlap volume, provided by a high resolution UV camera, are employed to resolve coupled rate equations accounting for two-photon excitation, fluorescence decay and ionization. The resulting three-dimensional yield distributions reveal in detail the spatial resolution for optogalvanic and LIF detection and related saturation due to depletion. Two-photon absorption profiles broader than the Fourier transform-limited laser bandwidth are also incorporated in the calculations. The approach allows an accurate analysis of the spatial resolution present in recent and future measurements.

  20. Shock-tube measurements of excited oxygen atoms using cavity-enhanced absorption spectroscopy.

    Nations, Marcel; Wang, Shengkai; Goldenstein, Christopher S; Sun, Kai; Davidson, David F; Jeffries, Jay B; Hanson, Ronald K

    2015-10-10

    We report the use of cavity-enhanced absorption spectroscopy (CEAS) using two distributed feedback diode lasers near 777.2 and 844.6 nm for sensitive, time-resolved, in situ measurements of excited-state populations of atomic oxygen in a shock tube. Here, a 1% O2/Ar mixture was shock-heated to 5400-8000 K behind reflected shock waves. The combined use of a low-finesse cavity, fast wavelength scanning of the lasers, and an off-axis alignment enabled measurements with 10 μs time response and low cavity noise. The CEAS absorption gain factors of 104 and 142 for the P35←S520 (777.2 nm) and P0,1,23←S310 (844.6 nm) atomic oxygen transitions, respectively, significantly improved the detection sensitivity over conventional single-pass measurements. This work demonstrates the potential of using CEAS to improve shock-tube studies of nonequilibrium electronic-excitation processes at high temperatures.

  1. [Influence of silver/silicon dioxide on infrared absorption spectroscopy of sodium nitrate].

    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

  2. Measurements of the mass absorption cross section of atmospheric soot particles using Raman spectroscopy

    Nordmann, S.; Birmili, W.; Weinhold, K.; Müller, K.; Spindler, G.; Wiedensohler, A.

    2013-11-01

    Soot particles are a major absorber of shortwave radiation in the atmosphere. The mass absorption cross section is an essential quantity to describe this light absorption process. This work presents new experimental data on the mass absorption cross section of soot particles in the troposphere over Central Europe. Mass absorption cross sections were derived as the ratio between the light absorption coefficient determined by multiangle absorption photometry (MAAP) and the soot mass concentration determined by Raman spectroscopy. The Raman method is sensitive to graphitic structures present in the particle samples and was calibrated in the laboratory using Printex®90 model particles. Mass absorption cross sections were determined for a number of seven observation sites, ranging between 3.9 and 7.4 m2 g-1depending on measurement site and observational period. The highest values were found in a continentally aged air mass in winter, where soot particles were assumed to be mainly internally mixed. Our values are in the lower range of previously reported values, possibly due to instrumental differences to the former photometer and mass measurements. Overall, a value of 5.3m2 g-1from orthogonal regression over all samples is considered to be representative for the soot mass absorption cross section in the troposphere over Central Europe.

  3. Pharmaceutical applications of separation of absorption and scattering in near-infrared spectroscopy (NIRS).

    Shi, Zhenqi; Anderson, Carl A

    2010-12-01

    The number of near-infrared (NIR) spectroscopic applications in the pharmaceutical sciences has grown significantly in the last decade. Despite its widespread application, the fundamental interaction between NIR radiation and pharmaceutical materials is often not mechanistically well understood. Separation of absorption and scattering in near-infrared spectroscopy (NIRS) is intended to extract absorption and scattering spectra (i.e., absorption and reduced scattering coefficients) from reflectance/transmittance NIR measurements. The purpose of the separation is twofold: (1) to enhance the understanding of the individual roles played by absorption and scattering in NIRS and (2) to apply the separated absorption and scattering spectra for practical spectroscopic analyses. This review paper surveys the multiple techniques reported to date on the separation of NIR absorption and scattering within pharmaceutical applications, focusing on the instrumentations, mathematical approaches used to separate absorption and scattering and related pharmaceutical applications. This literature review is expected to enhance the understanding and thereby the utility of NIRS in pharmaceutical science. Further, the measurement and subsequent understanding of the separation of absorption and scattering is expected to increase not only the number of NIRS applications, but also their robustness.

  4. Electronic absorption spectroscopy of PAHs in supersonic jets and ultracold liquid helium droplets

    Huisken, Friedrich; Staicu, Angela; Krasnokutski, Serge; Henning, Thomas

    Neutral and cationic polycyclic aromatic hydrocarbons (PAHs) are discussed as possible carriers of the diffuse interstellar bands (DIBs), still unassigned astrophysical absorption features observed in the spectra of reddened stars (Salama et al. 1999). Despite the importance of this class of molecules for astrophysics and nanophysics (PAHs can be regarded as nanoscale fragments of a sheet of graphite), the spectroscopic characterization of PAHs under well-defined conditions (low temperature and collision-free environment) has remained a challenge. Recently we have set up a cavity ring-down spectrometer combined with a pulsed supersonic jet expansion to study neutral and cationic PAHs under astrophysical conditions. PAHs studied so far include the neutral molecules anthracene (Staicu et al. 2004) and pyrene (Rouillé et al. 2004) as well as the cationic species naphthalene+ and anthracene+ (Sukhorukov et al. 2004). Employing another molecular beam apparatus, the same molecules (except of the cationic species) were also studied in liquid helium droplets (Krasnokutski et al. 2005, Rouillé et al. 2004). This novel technique combines several advantages of conventional matrix spectroscopy with those of gas phase spectroscopy. Notable advantages are the possibility to study molecules with low vapor pressure and to use a mass spectrometer facilitating spectral assignments. The most recent studies were devoted to phenanthrene and the more complicated (2,3)-benzofluorene. These molecules were investigated in the gas phase by cavity ring-down spectroscopy and in liquid helium droplets using depletion spectroscopy. For benzofluorene the present studies constitute the first reported measurements both in the gas phase and in helium droplets. The origin of the S1 ← S0 gas phase transition could be located at 29 894.3 cm-1, and a series of vibronic bands was recorded below 31 500 cm-1. In contrast to previously studied PAHs, the shift induced by the helium droplets was very

  5. Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

    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…

  6. Recovery of acetylene absorption line profile basing on tunable diode laser spectroscopy with intensity modulation and photoacoustic spectroscopy

    Li, Li; Thursby, Graham; Stewart, George; Arsad, Norhana; Uttamchandani, Deepak; Culshaw, Brian; Wang, Yiding

    2010-04-01

    A novel and direct absorption line recovery technique based on tunable diode laser spectroscopy with intensity modulation is presented. Photoacoustic spectroscopy is applied for high sensitivity, zero background and efficient acoustic enhancement at a low modulation frequency. A micro-electromechanical systems (MEMS) mirror driven by an electrothermal actuator is used for generating laser intensity modulation (without wavelength modulation) through the external reflection. The MEMS mirror with 10μm thick structure material layer and 100nm thick gold coating is formed as a circular mirror of 2mm diameter attached to an electrothermal actuator and is fabricated on a chip that is wire-bonded and placed on a PCB holder. Low modulation frequency is adopted (since the resonant frequencies of the photoacoustic gas cell and the electrothermal actuator are different) and intrinsic high signal amplitude characteristics in low frequency region achieved from measured frequency responses for the MEMS mirror and the gas cell. Based on the property of photoacoustic spectroscopy and Beer's law that detectable sensitivity is a function of input laser intensity in the case of constant gas concentration and laser path length, a Keopsys erbium doped fibre amplifier (EDFA) with opto-communication C band and high output power up to 1W is chosen to increase the laser power. High modulation depth is achieved through adjusting the MEMS mirror's reflection position and driving voltage. In order to scan through the target gas absorption line, the temperature swept method is adopted for the tunable distributed feed-back (DFB) diode laser working at 1535nm that accesses the near-infrared vibration-rotation spectrum of acetylene. The profile of acetylene P17 absorption line at 1535.39nm is recovered ideally for ~100 parts-per-million (ppm) acetylene balanced by nitrogen. The experimental signal to noise ratio (SNR) of absorption line recovery for 500mW laser power was ~80 and hence the

  7. Extending differential optical absorption spectroscopy for limb measurements in the UV

    Puä·Ä«Te, J.; Kühl, S.; Deutschmann, T.; Platt, U.; Wagner, T.

    2010-05-01

    Methods of UV/VIS absorption spectroscopy to determine the constituents in the Earth's atmosphere from measurements of scattered light are often based on the Beer-Lambert law, like e.g. Differential Optical Absorption Spectroscopy (DOAS). While the Beer-Lambert law is strictly valid for a single light path only, the relation between the optical depth and the concentration of any absorber can be approximated as linear also for scattered light observations at a single wavelength if the absorption is weak. If the light path distribution is approximated not to vary with wavelength, also linearity between the optical depth and the product of the cross-section and the concentration of an absorber can be assumed. These assumptions are widely made for DOAS applications for scattered light observations. For medium and strong absorption of scattered light (e.g. along very long light-paths like in limb geometry) the relation between the optical depth and the concentration of an absorber is no longer linear. In addition, for broad wavelength intervals the differences in the travelled light-paths at different wavelengths become important, especially in the UV, where the probability for scattering increases strongly with decreasing wavelength. However, the DOAS method can be extended to cases with medium to strong absorptions and for broader wavelength intervals by the so called air mass factor modified (or extended) DOAS and the weighting function modified DOAS. These approaches take into account the wavelength dependency of the slant column densities (SCDs), but also require a priori knowledge for the air mass factor or the weighting function from radiative transfer modelling. We describe an approach that considers the fitting results obtained from DOAS, the SCDs, as a function of wavelength and vertical optical depth and expands this function into a Taylor series of both quantities. The Taylor coefficients are then applied as additional fitting parameters in the DOAS analysis

  8. Extending differential optical absorption spectroscopy for limb measurements in the UV

    J. Puķīte

    2009-11-01

    Full Text Available Methods of UV/VIS absorption spectroscopy to determine the constituents in the Earth's atmosphere from measurements of scattered light are often based on the Beer-Lambert law, like e.g. Differential Optical Absorption Spectroscopy (DOAS. Therefore they are strictly valid for weak absorptions and narrow wavelength intervals (strictly only for monochromatic radiation. For medium and strong absorption (e.g. along very long light-paths like in limb geometry the relation between the optical depth and the concentration of an absorber is not linear anymore. As well, for large wavelength intervals the wavelength dependent differences in the travelled light-paths become important, especially in the UV, where the probability for scattering increases strongly with decreasing wavelength.

    However, by taking into account these dependencies, the applicability of the DOAS method can be extended also to cases with medium to strong absorptions and for broader wavelength intervals.

    Common approaches for this correction are the so called air mass factor modified (or extended DOAS and the weighting function modified DOAS. These approaches take into account the wavelength dependency of the slant column densities (SCDs, but also require a-priori knowledge for the air mass factor or the weighting function calculation by radiative transfer modelling.

    We describe an approach that considers the fitting results obtained from DOAS, the SCDs, as a function of wavelength and vertical optical depth and expands this function into a Taylor series of both quantities. The Taylor coefficients are then applied as additional fitting parameters in the DOAS analysis. Thus the variability of the SCD in the fit window is determined by the retrieval itself.

    This new approach gives a description of the SCD that is as close to reality as desired (depending on the order of the Taylor expansion, and is independent from any assumptions or a-priori knowledge

  9. Extending differential optical absorption spectroscopy for limb measurements in the UV

    J. Puķīte

    2010-05-01

    Full Text Available Methods of UV/VIS absorption spectroscopy to determine the constituents in the Earth's atmosphere from measurements of scattered light are often based on the Beer-Lambert law, like e.g. Differential Optical Absorption Spectroscopy (DOAS. While the Beer-Lambert law is strictly valid for a single light path only, the relation between the optical depth and the concentration of any absorber can be approximated as linear also for scattered light observations at a single wavelength if the absorption is weak. If the light path distribution is approximated not to vary with wavelength, also linearity between the optical depth and the product of the cross-section and the concentration of an absorber can be assumed. These assumptions are widely made for DOAS applications for scattered light observations.

    For medium and strong absorption of scattered light (e.g. along very long light-paths like in limb geometry the relation between the optical depth and the concentration of an absorber is no longer linear. In addition, for broad wavelength intervals the differences in the travelled light-paths at different wavelengths become important, especially in the UV, where the probability for scattering increases strongly with decreasing wavelength.

    However, the DOAS method can be extended to cases with medium to strong absorptions and for broader wavelength intervals by the so called air mass factor modified (or extended DOAS and the weighting function modified DOAS. These approaches take into account the wavelength dependency of the slant column densities (SCDs, but also require a priori knowledge for the air mass factor or the weighting function from radiative transfer modelling.

    We describe an approach that considers the fitting results obtained from DOAS, the SCDs, as a function of wavelength and vertical optical depth and expands this function into a Taylor series of both quantities. The Taylor coefficients are then applied as

  10. Decays of the Three Top Contributors to the Reactor ν¯e High-Energy Spectrum, 92Rb, Ygs96 , and 142Cs, Studied with Total Absorption Spectroscopy

    Rasco, B. C.; Wolińska-Cichocka, M.; Fijałkowska, A.; Rykaczewski, K. P.; Karny, M.; Grzywacz, R. K.; Goetz, K. C.; Gross, C. J.; Stracener, D. W.; Zganjar, E. F.; Batchelder, J. C.; Blackmon, J. C.; Brewer, N. T.; Go, S.; Heffron, B.; King, T.; Matta, J. T.; Miernik, K.; Nesaraja, C. D.; Paulauskas, S. V.; Rajabali, M. M.; Wang, E. H.; Winger, J. A.; Xiao, Y.; Zachary, C. J.

    2016-08-01

    We report total absorption spectroscopy measurements of 92Rb, Ygs96 , and 142Cs β decays, which are the most important contributors to the high energy ν¯e spectral shape in nuclear reactors. These three β decays contribute 43% of the ν¯e flux near 5.5 MeV emitted by nuclear reactors. This ν¯e energy is particularly interesting due to spectral features recently observed in several experiments including the Daya Bay, Double Chooz, and RENO Collaborations. Measurements were conducted at Oak Ridge National Laboratory by means of proton-induced fission of 238U with on-line mass separation of fission fragments and the Modular Total Absorption Spectrometer. We observe a β -decay pattern that is similar to recent measurements of 92Rb, with a ground-state to ground-state β feeding of 91(3)%. We verify the Ygs96 ground-state to ground-state β feeding of 95.5(20)%. Our measurements substantially modify the β -decay feedings of 142Cs, reducing the β feeding to 142Ba states below 2 MeV by 32% when compared with the latest evaluations. Our results increase the discrepancy between the observed and the expected reactor ν¯e flux between 5 and 7 MeV, the maximum excess increases from ˜10 % to ˜12 %.

  11. Decays of the Three Top Contributors to the Reactor ν[over ¯]_{e} High-Energy Spectrum, ^{92}Rb, ^{96gs}Y, and ^{142}Cs, Studied with Total Absorption Spectroscopy.

    Rasco, B C; Wolińska-Cichocka, M; Fijałkowska, A; Rykaczewski, K P; Karny, M; Grzywacz, R K; Goetz, K C; Gross, C J; Stracener, D W; Zganjar, E F; Batchelder, J C; Blackmon, J C; Brewer, N T; Go, S; Heffron, B; King, T; Matta, J T; Miernik, K; Nesaraja, C D; Paulauskas, S V; Rajabali, M M; Wang, E H; Winger, J A; Xiao, Y; Zachary, C J

    2016-08-26

    We report total absorption spectroscopy measurements of ^{92}Rb, ^{96gs}Y, and ^{142}Cs β decays, which are the most important contributors to the high energy ν[over ¯]_{e} spectral shape in nuclear reactors. These three β decays contribute 43% of the ν[over ¯]_{e} flux near 5.5 MeV emitted by nuclear reactors. This ν[over ¯]_{e} energy is particularly interesting due to spectral features recently observed in several experiments including the Daya Bay, Double Chooz, and RENO Collaborations. Measurements were conducted at Oak Ridge National Laboratory by means of proton-induced fission of ^{238}U with on-line mass separation of fission fragments and the Modular Total Absorption Spectrometer. We observe a β-decay pattern that is similar to recent measurements of ^{92}Rb, with a ground-state to ground-state β feeding of 91(3)%. We verify the ^{96gs}Y ground-state to ground-state β feeding of 95.5(20)%. Our measurements substantially modify the β-decay feedings of ^{142}Cs, reducing the β feeding to ^{142}Ba states below 2 MeV by 32% when compared with the latest evaluations. Our results increase the discrepancy between the observed and the expected reactor ν[over ¯]_{e} flux between 5 and 7 MeV, the maximum excess increases from ∼10% to ∼12%.

  12. The dependence of the ultrafast relaxation kinetics of the S2 and S1 states in β-carotene homologs and lycopene on conjugation length studied by femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies

    Kosumi, Daisuke; Fujiwara, Masazumi; Fujii, Ritsuko; Cogdell, Richard J.; Hashimoto, Hideki; Yoshizawa, Masayuki

    2009-06-01

    The ultrafast relaxation kinetics of all-trans-β-carotene homologs with varying numbers of conjugated double bonds n(n =7-15) and lycopene (n =11) has been investigated using femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies, both carried out under identical excitation conditions. The nonradiative relaxation rates of the optically allowed S2(1Bu+1) state were precisely determined by the time-resolved fluorescence. The kinetics of the optically forbidden S1(2Ag-1) state were observed by the time-resolved absorption measurements. The dependence of the S1 relaxation rates upon the conjugation length is adequately described by application of the energy gap law. In contrast to this, the nonradiative relaxation rates of S2 have a minimum at n =9 and show a reverse energy gap law dependence for values of n above 11. This anomalous behavior of the S2 relaxation rates can be explained by the presence of an intermediate state (here called the Sx state) located between the S2 and S1 states at large values of n (such as n =11). The presence of such an intermediate state would then result in the following sequential relaxation pathway S2→Sx→S1→S0. A model based on conical intersections between the potential energy curves of these excited singlet states can readily explain the measured relationships between the decay rates and the energy gaps.

  13. Soft X-ray absorption and photoemission spectroscopy study of semiconductor oxide nanoparticles for dye-sensitized solar cell: ZnSnO3 and Zn2SnO4

    Kim, Hyun Woo; Lee, Eunsook; Kim, D. H.; Seong, Seungho; Moon, Soo Yeon; Shin, Yu-Ju; Baik, J.; Shin, H. J.; Kang, J.-S.

    2016-06-01

    The electronic structures of the Zn-stannate nanoparticles of ZnSnO3 and Zn2SnO4, which are the potential nano-structured semiconductor oxides for a dye sensitized solar cell (DSSC), have been investigated by employing photoemission spectroscopy (PES) and soft X-ray absorption spectroscopy (XAS), and compared to those of reference materials. The divalent and tetravalent valence states of Zn2+ and Sn4+ ions are confirmed experimentally. The energy levels of both the valence-band and conduction-band edges are determined experimentally. The top of the valence band in PES is slightly higher in Zn2SnO4 than in ZnSnO3. The onset energies of the O 1s XAS spectra of the Zn-stannates are found to be similar to each other, but higher than that of TiO2. The O 1 s XAS spectrum of ZnSnO3 exhibits the higher unoccupied density of states near the bottom of the conduction band than those of Zn2SnO4, SnO2 and ZnO, reflecting the larger number of holes in the Zn 3 d bands of ZnSnO3. Hence, the easier electron transfer is expected from the LUMO (lowest unoccupied molecular orbital) of a dye molecule to the conduction band of ZnSnO3 nanoparticles on the transparent conductive electrode of a DSSC.

  14. O-vacancies in (i) nano-crystalline HfO2 and (i) non-crystalline SiO2 and Si3N4 studied by X-ray absorption spectroscopy.

    Lucovsky, Gerald; Miotti, Leonardo; Bastos, Karen Paz

    2012-06-01

    Performance and reliability in semiconductor devices are limited by electronically active defects, primarily O-atom and N-atom vacancies. Synchrotron X-ray spectroscopy results, interpreted in the context of two-electron multiplet theories, have been used to analyze conduction band edge, and O-vacancy defect states in nano-crystalline transition metal oxides, e.g., HfO2, and the noncrystalline dielectrics, SiO2, Si3N4 and Si-oxynitride alloys. Two-electron multiplet theory been used to develop a high-spin state equivalent d2 model for O-vacancy allowed transitions and negative ion states as detected by X-ray absorption spectroscopy in the O K pre-edge regime. Comparisons between theory and experiment have used Tanabe-Sugano energy level diagrams for determining the symmetries and relative energies of intra-d-state transitions for an equivalent d2 ground state occupancy. Trap-assisted-tunneling, Poole-Frenkel hopping transport, and the negative bias temperature instability have been explained in terms of injection and/or trapping into O-atom and N-atom vacancy sites, and applied to gate dielectric, and metal-insulator-metal structures.

  15. Minute Concentration Measurements of Simple Hydrocarbon Species Using Supercontinuum Laser Absorption Spectroscopy.

    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.

  16. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

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

    1995-06-01

    This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

  17. Absorption spectroscopy at the ultimate quantum limit from single-photon states

    Whittaker, R.; Erven, C.; Neville, A.; Berry, M.; O’Brien, J. L.; Cable, H.; Matthews, J. C. F.

    2017-02-01

    Absorption spectroscopy is routinely used to characterise chemical and biological samples. For the state-of-the-art in laser absorption spectroscopy, precision is theoretically limited by shot-noise due to the fundamental Poisson-distribution of photon number in laser radiation. In practice, the shot-noise limit can only be achieved when all other sources of noise are eliminated. Here, we use wavelength-correlated and tuneable photon pairs to demonstrate how absorption spectroscopy can be performed with precision beyond the shot-noise limit and near the ultimate quantum limit by using the optimal probe for absorption measurement—single photons. We present a practically realisable scheme, which we characterise both the precision and accuracy of by measuring the response of a control feature. We demonstrate that the technique can successfully probe liquid samples and using two spectrally similar types of haemoglobin we show that obtaining a given precision in resolution requires fewer heralded single probe photons compared to using an idealised laser.

  18. Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

    Alexander Klein

    2014-11-01

    Full Text Available 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.

  19. Near Edge X-Ray Absorption Fine Structure Spectroscopy with X-Ray Free-Electron Lasers

    Bernstein, D.P.; Acremann, Y.; Scherz, A.; Burkhardt, M.; Stohr, J.; /SLAC; Beye, M.; Schlotter, W.F.; Beeck, T.; Sorgenfrei, F.; Pietzsch, A.; Wurth, W.; Fohlisch, A.; /Hamburg U.

    2009-12-11

    We demonstrate the feasibility of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy on solids by means of femtosecond soft x-ray pulses from a free-electron laser (FEL). Our experiments, carried out at the Free-Electron Laser at Hamburg (FLASH), used a special sample geometry, spectrographic energy dispersion, single shot position-sensitive detection and a data normalization procedure that eliminates the severe fluctuations of the incident intensity in space and photon energy. As an example we recorded the {sup 3}D{sub 1} N{sub 4,5}-edge absorption resonance of La{sup 3+}-ions in LaMnO{sub 3}. Our study opens the door for x-ray absorption measurements on future x-ray FEL facilities.

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

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

    2016-06-01

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

  1. Force spectroscopy in studying infection

    Zhou, Zhaokun

    2016-01-01

    Biophysical force spectroscopy tools - for example optical tweezers, magnetic tweezers, atomic force microscopy, - have been used to study elastic, mechanical, conformational and dynamic properties of single biological specimens from single proteins to whole cells to reveal information not accessible by ensemble average methods such as X-ray crystallography, mass spectroscopy, gel electrophoresis and so on. Here we review the application of these tools on a range of infection-related questions from antibody-inhibited protein processivity to virus-cell adhesion. In each case we focus on how the instrumental design tailored to the biological system in question translates into the functionality suitable for that particular study. The unique insights that force spectroscopy has gained to complement knowledge learned through population averaging techniques in interrogating biomolecular details prove to be instrumental in therapeutic innovations such as those in structure-based drug design.

  2. Reconstruction of combustion temperature and gas concentration distributions using line-of-sight tunable diode laser absorption spectroscopy

    Zhang, Zhirong; Sun, Pengshuai; Pang, Tao; Xia, Hua; Cui, Xiaojuan; Li, Zhe; Han, Luo; Wu, Bian; Wang, Yu; Sigrist, Markus W.; Dong, Fengzhong

    2016-07-01

    Spatial temperature and gas concentration distributions are crucial for combustion studies to characterize the combustion position and to evaluate the combustion regime and the released heat quantity. Optical computer tomography (CT) enables the reconstruction of temperature and gas concentration fields in a flame on the basis of line-of-sight tunable diode laser absorption spectroscopy (LOS-TDLAS). A pair of H2O absorption lines at wavelengths 1395.51 and 1395.69 nm is selected. Temperature and H2O concentration distributions for a flat flame furnace are calculated by superimposing two absorption peaks with a discrete algebraic iterative algorithm and a mathematical fitting algorithm. By comparison, direct absorption spectroscopy measurements agree well with the thermocouple measurements and yield a good correlation. The CT reconstruction data of different air-to-fuel ratio combustion conditions (incomplete combustion and full combustion) and three different types of burners (one, two, and three flat flame furnaces) demonstrate that TDLAS has the potential of short response time and enables real-time temperature and gas concentration distribution measurements for combustion diagnosis.

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

    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.

  4. Absorption spectroscopy measurements in optically dense explosive fireballs using a modeless broadband dye laser.

    Glumac, Nick

    2009-09-01

    A modeless broadband dye laser is applied to probe inside optically dense fireballs generated by high explosives using single-shot, high resolution absorption spectroscopy. Despite attenuation of the main beam by 98%, high signal-to-noise ratio absorption spectra of Al, Ti, and AlO are readily obtained at resolutions of 0.007 nm, and luminosity from the fireball is strongly rejected. Detection limits for atomic species are less than 200 ppb. The method offers good time resolution of chemistry within the fireball, and scaling laws suggest that this technique should be valid in explosives tests at least up to the gram scale.

  5. The molecular and electronic states of 1,2,4,5-tetrazine studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction studies

    Palmer, Michael H.; McNab, Hamish; Reed, David; Pollacchi, Anne; Walker, Isobel C.; Guest, Martyn F.; Siggel, Michele R. F.

    1997-01-01

    The VUV electronic absorption spectrum of 1,2,4,5-tetrazine has been re-investigated, and together with electron energy-loss spectra has led to identification of a number of new excited states. The valence and Rydberg excited states have been studied by multi-reference multi-root configuration interaction studies using MRDCI techniques. Initial studies with the RPA and TDA methods gave almost identical results for the excitation energies, but there is a substantial energy-lowering in the MRDCI calculations, which improves agreement with experiment substantially; these differences are a result of the double, triple and quadruple excited reference configurations included in the reference set of the latter method. The 1ππ ∗ excitations are calculated rather higher than experiment, except for the lowest-lying (weak) 1B 2u state at 5.0 eV. The calculated order for the next three ππ ∗ states is 1B 1u (weak) followed by 1B 2u (strong) and 1B 1u (strong), the last two bands being responsible for the dominant absorption near 7.5 and 8.5 eV. All of this group of four bands involve excitations from the pair of MOs 1b 2g and 1b 1g into the 1a u∗ and 4b 3u∗ VMOs. The sequence of nπ ∗ stakes are in a similar order to the ππ ∗ excitations, with respect to the upper state, and the two lowest singlet states, 1B 3u and 1A u are reasonably well determined. The triplet states follow a similar order to the singlets, and again the dominance of the effect of the two lowest VMOs is demonstrated, but considerable differences between the weighting of leading configurations occurs between singlet and triplet manifolds. The non-diagonal TDA method has been used to reconsider the UV-photoelectron spectrum. The ionisation potentials for tetrazine are reinterpreted with the first three bands being regrouped into 1, 2, 2 ionisations respectively. The ground state properties of tetrazine suggest that the NQR spectrum will show a principal axis 14N quadrupole coupling constant

  6. Infrared absorption spectroscopy of the COAr complex

    McKellar, A. R. W.; Zeng, Y. P.; Sharpe, S. W.; Wittig, C.; Beaudet, R. A.

    1992-05-01

    The rotation-vibration spectrum of the weakly bound complex COAr has been studied in the 2140 cm -1 region of the fundamental band of CO. Data were obtained from two different experiments: first, a pulsed slit-jet supersonic expansion and a tunable diode laser source; and second a long-path low-temperature static gas cell and a Fourier transform spectrometer. The low rotational temperature and narrow line width of the jet expansion data were complementary to the higher J-values and broad coverage of the static cell data. The observed spectrum was approximately that of a T-shaped near-prolate asymmetric rotor molecule. About 370 transitions were assigned to 6 perpendicular subbands with K = 3-2, 2-1, 1-0, 0-1, 1-2, and 2-3. No parallel (Δ K = 0) subbands were observed. The observed B rotational constant of the complex in its ground state, 0.0691 cm -1, corresponds to an effective intermolecular separation of about 3.850 Å. The observed A rotational constant of about 2.47 cm -1 is not too far from the overlineB value of the CO monomer, 1.92 cm -1, as expected for the approximately T-shaped effective geometry of the complex.

  7. Capturing molecular structural dynamics by 100 ps time-resolved X-ray absorption spectroscopy

    Sato, Tokushi [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Nozawa, Shunsuke; Ichiyanagi, Kohei [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Tomita, Ayana [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Chollet, Matthieu [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Ichikawa, Hirohiko [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Fujii, Hiroshi [Institute for Molecular Science and Okazaki Institute for Integrative Bioscience, Myodaiji, Okazaki 444-8787 (Japan); Adachi, Shin-ichi [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Koshihara, Shin-ya, E-mail: skoshi@cms.titech.ac.jp [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Frontier Research Center, Tokyo Institute of Technology, 2-12-1 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan)

    2009-01-01

    An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. The X-ray positional active feedback to crystals in a monochromator combined with a figure-of-merit scan of the laser beam position has been utilized as an essential tool to stabilize the spatial overlap of the X-ray and laser beams at the sample position. As a typical example, a time-resolved XAFS measurement of a photo-induced spin crossover reaction of the tris(1,10-phenanthrorine)iron(II) complex in water is presented.

  8. Determination of vanadium in food and traditional Chinese medicine by graphite furnace atomic absorption spectroscopy

    2003-01-01

    Various experimental conditions were described for the vanadium determination by graphite furnace atomic ab-sorption spectroscopy (GFAAS). The experiments showed that when atomization took place under the conditions where thecombination of a pyrolytic coating graphite tube and fast raising temperature were used and the temperature was stable, thesignal peak shapes could be improved, the sensitivity was enhanced, and the memory effect was removed. The vanadium infood and traditional Chinese medicinal herbs can be accurately determined using the standard curve method.

  9. A quantum perturbative pair distribution for determining interatomic potentials from extended X-ray absorption spectroscopy

    Piazza, Francesco

    2002-01-01

    In this paper we develop a technique for determining interatomic potentials in materials in the quantum regime from single--shell Extended X-ray Absorption Spectroscopy (EXAFS) spectra. We introduce a pair distribution function, based on ordinary quantum time--independent perturbation theory. In the proposed scheme, the model potential parameters enter the distribution through a fourth--order Taylor expansion of the potential, and are directly refined in the fit of the model signal to the exp...

  10. Application of microemulsions in determination of chromium naphthenate in gasoline by flame atomic absorption spectroscopy.

    Du, B; Wei, Q; Wang, S; Yu, W

    1997-10-01

    A new method using microemulsified samples is presented. It is for the determination of chromium naphthenate in gasoline by flame absorption spectroscopy. The method has the advantage of simplicity, speed and the use of aqueous standards for calibration instead of organic standards. Coexistent elements do not disturb the determination. Results obtained by this method were better than those obtained by other methods for the same samples.

  11. Surface-enhanced infrared absorption spectroscopy (SEIRAS) to probe monolayers of membrane proteins.

    Ataka, Kenichi; Stripp, Sven Timo; Heberle, Joachim

    2013-10-01

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) represents a variation of conventional infrared spectroscopy and exploits the signal enhancement exerted by the plasmon resonance of nano-structured metal thin films. The surface enhancement decays in about 10nm with the distance from the surface and is, thus, perfectly suited to selectively probe monolayers of biomembranes. Peculiar to membrane proteins is their vectorial functionality, the probing of which requires proper orientation within the membrane. To this end, the metal surface used in SEIRAS is chemically modified to generate an oriented membrane protein film. Monolayers of uniformly oriented membrane proteins are formed by tethering His-tagged proteins to a nickel nitrilo-triacetic acid (Ni-NTA) modified gold surface and SEIRAS commands molecular sensitivity to probe each step of surface modification. The solid surface used as plasmonic substrate for SEIRAS, can also be employed as an electrode to investigate systems where electron transfer reactions are relevant, like e.g. cytochrome c oxidase or plant-type photosystems. Furthermore, the interaction of these membrane proteins with water-soluble proteins, like cytochrome c or hydrogenase, is studied on the molecular level by SEIRAS. The impact of the membrane potential on protein functionality is verified by monitoring light-dark difference spectra of a monolayer of sensory rhodopsin (SRII) at different applied potentials. It is demonstrated that the interpretations of all of these experiments critically depend on the orientation of the solid-supported membrane protein. Finally, future directions of SEIRAS including cellular systems are discussed. This article is part of a Special Issue entitled: FTIR in membrane proteins and peptide studies.

  12. Adding diffuse reflectance infrared Fourier transform spectroscopy capability to extended x-ray-absorption fine structure in a new cell to study solid catalysts in combination with a modulation approach

    Chiarello, Gian Luca [Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, I-20133 Milano, Italy and Empa, Swiss Federal Laboratories for Materials Science and Technology, Lab. for Solid State Chemistry and Catalysis, Ueberlandstrasse 129, CH-8600 Dübendorf (Switzerland); Nachtegaal, Maarten; Marchionni, Valentina; Quaroni, Luca; Ferri, Davide, E-mail: davide.ferri@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland)

    2014-07-15

    We describe a novel cell used to combine in situ transmission X-ray absorption spectroscopy (XAS) with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in a single experiment. The novelty of the cell design compared to current examples is that both radiations are passed through an X-ray and IR transparent window in direct contact with the sample. This innovative geometry also offers a wide surface for IR collection. In order to avoid interference from the crystalline IR transparent materials (e.g., CaF{sub 2}, MgF{sub 2}, diamond) a 500 μm carbon filled hole is laser drilled in the center of a CaF{sub 2} window. The cell is designed to represent a plug flow reactor, has reduced dead volume in order to allow for fast exchange of gases and is therefore suitable for experiments under fast transients, e.g., according to the concentration modulation approach. High quality time-resolved XAS and DRIFTS data of a 2 wt.% Pt/Al{sub 2}O{sub 3} catalyst are obtained in concentration modulation experiments where CO (or H{sub 2}) pulses are alternated to O{sub 2} pulses at 150 °C. We show that additional information can be obtained on the Pt redox dynamic under working conditions thanks to the improved sensitivity given by the modulation approach followed by Phase Sensitive Detection (PSD) analysis. It is anticipated that the design of the novel cell is likely suitable for a number of other in situ spectroscopic and diffraction methods.

  13. X-ray absorption and emission spectroscopy study of Mn and Co valence and spin states in TbM n1 -xC oxO3

    Cuartero, V.; Lafuerza, S.; Rovezzi, M.; García, J.; Blasco, J.; Subías, G.; Jiménez, E.

    2016-10-01

    The valence and spin state evolution of Mn and Co on TbM n1 -xC oxO3 series is precisely determined by means of soft and hard x-ray absorption spectroscopy (XAS) and K β x-ray emission spectroscopy (XES). Our results show the change from M n3 + to M n4 + both high-spin (HS) together with the evolution from C o2 + HS to C o3 + low-spin (LS) with increasing x . In addition, high energy resolution XAS spectra on the K pre-edge region are interpreted in terms of the strong charge transfer and hybridization effects along the series. These results correlate well with the spin values of Mn and Co atoms obtained from the K β XES data. In this paper, we determine that Co enters into the transition metal sublattice of TbMn O3 as a divalent ion in HS state, destabilizing the Mn long-range magnetic order since very low doping compositions (x ≤0.1 ). Samples in the intermediate composition range (0.4 ≤x ≤0.6 ) adopt the crystal structure of a double perovskite with long-range ferromagnetic ordering which is due to M n4 + -O-C o2 + superexchange interactions with both cations in HS configuration. Ferromagnetism vanishes for x ≥0.7 due to the structural disorder that collapses the double perovskite structure. The spectroscopic techniques reveal the occurrence of M n4 + HS and a fluctuating valence state C o2 + HS/C o3 + LS in this composition range. Disorder and competitive interactions lead to a magnetic glassy behavior in these samples.

  14. An approach of open-path gas sensor based on tunable diode laser absorption spectroscopy

    Hui Xia; Wenqing Liu; Yujun Zhang; Ruifeng Kan; Min Wang; Ying He; Yiben Cui; Jun Ruan; Hui Geng

    2008-01-01

    Tunable diode laser absorption spectroscopy (TDLAS) is a new method to detect trace-gas qualitatively or quantificationally based on the scan characteristic of the diode laser to obtain the absorption spectroscopy in the characteristic absorption region. A time-sharing scanning open-path TDLAS system using two near infrared distributed feedback (DFB) tunable diode lasers is designed to detect CH4 and H2S in leakage of natural gas. A low-cost Fresnel lens is used in this system as receiving optics which receives the laser beam reflected by a solid corner cube reflector with a distance of up to about 60 m. High sensitivity is achieved by means of wavelength-modulation spectroscopy with second-harmonic detection. The minimum detection limits of 1.1 ppm·m for CH4 and 15 ppm·m for H2S are demonstrated with a total optical path of 120 m. The simulation monitoring experiment of nature gas leakage was carried out with this system. According to the receiving light efficiency of optical system and detectable minimum light intensity of detection, the detectable optical path of the system can achieve 1 - 2 km. The sensor is suitable for natural gas leakage monitoring application.

  15. CdS-Sensitized ZnO Nanorod Photoelectrodes: Photoelectrochemistry and Photoinduced Absorption Spectroscopy

    Idriss Bedja

    2011-01-01

    Full Text Available Thin films of ZnO semiconductor nanorods (ZnO-nr of 6 μm length and thin ZnO nanoparticulate films (ZnO-np have been prepared and modified with Q-dots CdS for comparison study. PIA (photoinduced absorption spectroscopy, a multipurpose tool in the study of dye-sensitized solar cells, is used to study a quantum-dot-modified metal-oxide nanostrucutred electrode. Q-dot CdS-sensitized ZnO-nr (1D network sensitized photoelectrode has demonstrated best performances in both photoelectrical response (IPCE max = 92% and broadening response into far visible comparing to ZnO-np-based CdS solar cell. Preadsorbing ZnO-nr with ZnO-np does not bring further improvement. Time constant for electron injection into ZnO-nr conduction band was relatively fast decay of 6.5 ms, similar to TiO2-coated CdS, and proves at least a well pore filling of ZnO-nr film by ultrafine CdS particles. Unidirectional electron transfer mechanistic in ZnO-nr has played a major role in these performances.

  16. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J., E-mail: saykally@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Shih, Orion [National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China); Rizzuto, Anthony M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Prendergast, David [The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-08-28

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

  17. X-ray absorption and X-ray emission spectroscopy theory and applications

    Lamberti, Carlo

    2016-01-01

    During the last two decades, remarkable and often spectacular progress has been made in the methodological and instrumental aspects of x–ray absorption and emission spectroscopy. This progress includes considerable technological improvements in the design and production of detectors especially with the development and expansion of large-scale synchrotron reactors All this has resulted in improved analytical performance and new applications, as well as in the perspective of a dramatic enhancement in the potential of x–ray based analysis techniques for the near future. This comprehensive two-volume treatise features articles that explain the phenomena and describe examples of X–ray absorption and emission applications in several fields, including chemistry, biochemistry, catalysis, amorphous and liquid systems, synchrotron radiation, and surface phenomena. Contributors explain the underlying theory, how to set up X–ray absorption experiments, and how to analyze the details of the resulting spectra. X-R...

  18. Gas trace detection with cavity enhanced absorption spectroscopy: a review of its process in the field

    Liu, Siqi; Luo, Zhifu; Tan, Zhongqi; Long, Xingwu

    2016-11-01

    Cavity-enhanced absorption spectroscopy (CEAS) is a technology in which the intracavity absorption is deduced from the intensity of light transmitted by the high finesse optical cavity. Then the samples' parameters, such as their species, concentration and absorption cross section, would be detection. It was first proposed and demonstrated by Engeln R. [1] and O'Keefe[2] in 1998. This technology has extraordinary detection sensitivity, high resolution and good practicability, so it is used in many fields , such as clinical medicine, gas detection and basic physics research. In this paper, we focus on the use of gas trace detection, including the advance of CEAS over the past twenty years, the newest research progresses, and the prediction of this technology's development direction in the future.

  19. Mid-infrared laser absorption spectroscopy of NO2 at elevated temperatures

    Sur, Ritobrata; Peng, Wen Yu; Strand, Christopher; Mitchell Spearrin, R.; Jeffries, Jay B.; Hanson, Ronald K.; Bekal, Anish; Halder, Purbasha; Poonacha, Samhitha P.; Vartak, Sameer; Sridharan, Arun K.

    2017-01-01

    A mid-infrared quantum cascade laser absorption sensor was developed for in-situ detection of NO2 in high-temperature gas environments. A cluster of spin-split transitions near 1599.9 cm-1 from the ν3 absorption band of NO2 was selected due to the strength of these transitions and the low spectral interference from water vapor within this region. Temperature- and species-dependent collisional broadening parameters of ten neighboring NO2 transitions with Ar, O2, N2, CO2 and H2O were measured and reported. The spectral model was validated through comparisons with direct absorption spectroscopy measurements of NO2 seeded in various bath gases. The performance of the scanned wavelength modulation spectroscopy (WMS)-based sensor was demonstrated in a combustion exhaust stream seeded with varying flow rates of NO2, achieving reliable detection of 1.45 and 1.6 ppm NO2 by mole at 600 K and 800 K, respectively, with a measurement uncertainty of ±11%. 2σ noise levels of 360 ppb and 760 ppb were observed at 600 K and 800 K, respectively, in an absorption path length of 1.79 m.

  20. Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy.

    Wang, Dongxing; Zhu, Wenqi; Best, Michael D; Camden, Jon P; Crozier, Kenneth B

    2013-10-04

    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.

  1. Study of anomalous temperature dependence of itinerant holes in under- and overdoped La sub 2 sub - sub x Sr sub x CuO sub 4 single crystals using polarised soft X-ray absorption spectroscopy

    Singhal, R K; Dalela, S; Sekhar, B; Jain, D C; Garg, K B

    2003-01-01

    Some experiments have recently shown that in the YBCO detwinned system charge aggregation takes place in the Cu-O sub 2 plane along the b-axis at T>>T sub c followed by formation of Cooper pairs, again in the normal state. Polarised X-ray absorption measurements at the O K and Cu L sub 3 absorption edges in E parallel b orientation have been carried out on underdoped and overdoped single crystals of La sub 2 sub - sub x Sr sub x CuO sub 4 through a temperature range of 10-300 K to study the dependence of the itinerant hole density. Both the crystals do show an anomalous temperature dependence but there is a wide divergence in the earlier and our results. This paper discusses the results and possible causes for the difference.

  2. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

  3. Spectroscopic study of low-temperature hydrogen absorption in palladium

    Ienaga, K., E-mail: ienaga@issp.u-tokyo.ac.jp; Takata, H.; Onishi, Y.; Inagaki, Y.; Kawae, T. [Department of Applied Quantum Physics, Faculty of Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka 819-0395 (Japan); Tsujii, H. [Department of Physics, Faculty of Education, Kanazawa University, Kakuma-machi, Kanazawa 920-1192 (Japan); Kimura, T. [Department of Physics, Kyushu University, Hakozaki, Higashi-Ku, Fukuoka 812-8581 (Japan)

    2015-01-12

    We report real-time detection of hydrogen (H) absorption in metallic palladium (Pd) nano-contacts immersed in liquid H{sub 2} using inelastic electron spectroscopy (IES). After introduction of liquid H{sub 2}, the spectra exhibit the time evolution from the pure Pd to the Pd hydride, indicating that H atoms are absorbed in Pd nano-contacts even at the temperature where the thermal process is not expected. The IES time and bias voltage dependences show that H absorption develops by applying bias voltage 30 ∼ 50 mV, which can be explained by quantum tunneling. The results represent that IES is a powerful method to study the kinetics of high density H on solid surface.

  4. Charge Carrier Dynamics of Quantum Confined Semiconductor Nanoparticles Analyzed via Transient Absorption Spectroscopy

    Thibert, Arthur Joseph, III

    Semiconductor nanoparticles are tiny crystalline structures (typically range from 1 - 100 nm) whose shape in many cases can be dictated through tailored chemical synthesis with atomic scale precision. The small size of these nanoparticles often results in quantum confinement (spatial confinement of wave functions), which imparts the ability to manipulate band-gap energies thus allowing them to be optimally engineered for different applications (i.e., photovoltaics, photocatalysis, imaging). However, charge carriers excited within these nanoparticles are often involved in many different processes: trapping, trap migration, Auger recombination, non-radiative relaxation, radiative relaxation, oxidation / reduction, or multiple exciton generation. Broadband ultrafast transient absorption laser spectroscopy is used to spectrally resolve the fate of excited charge carriers in both wavelength and time, providing insight as to what synthetic developments or operating conditions will be necessary to optimize their efficiency for certain applications. This thesis outlines the effort of resolving the dynamics of excited charge carriers for several Cd and Si based nanoparticle systems using this experimental technique. The thesis is organized into five chapters and two appendices as indicated below. Chapter 1 provides a brief introduction to the photophysics of semiconductor nanoparticles. It begins by defining what nanoparticles, semiconductors, charge carriers, and quantum confinement are. From there it details how the study of charge carrier dynamics within nanoparticles can lead to increased efficiency in applications such as photocatalysis. Finally, the experimental methodology associated with ultrafast transient absorption spectroscopy is introduced and its power in mapping charge carrier dynamics is established. Chapter 2 (JPCC, 19647, 2011) introduces the first of the studied samples: water-solubilized 2D CdSe nanoribbons (NRs), which were synthesized in the Osterloh

  5. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  6. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    Taga, Raijeli L.; Zheng, Jiajia; Huynh, Trang; Ng, Jack; Harris, Hugh H.; Noller, Barry

    2010-06-01

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe6(SO4)4(OH)12) by lead L3-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM10 particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  7. An X-ray Absorption Spectroscopy Study of the Cathodic Discharge of Ag2VO2PO4: Geometric and Electronic Structure Characterization of Intermediate Phases and Mechanistic Insights

    C Patridge; C Jaye; T Abtew; B Ravel; D Fischer; A Marschilok; P Zhang; K Takeuchi; E Takeuchi; S Baneerjee

    2011-12-31

    Bimetallic phosphorus oxides have emerged as attractive candidates for use as cathode materials in the next generation of lithium-based batteries owing to the operation of multielectron transfer processes and thermochemical stabilities conferred by the incorporation of phosphate groups. In particular silver vanadium phosphorus oxide, Ag{sub 2}VO{sub 2}PO{sub 4}, shows a much desired in situ conductivity enhancement upon discharge resulting in inherently high power capability with minimal conductive additives needed. However, the amorphization of Ag{sub 2}VO{sub 2}PO{sub 4} during electrochemical discharge precludes the use of standard diffraction tools to monitor changes in the local electronic and geometric structure. Here, we have utilized a combination of V K-, V L-, Ag K-, and O K-edge X-ray absorption fine structure spectroscopy to determine the local vanadium and silver oxidation states, local coordination geometry, and stoichiometry for Ag{sub 2}VO{sub 2}PO{sub 4} samples with varying extents of electrochemical lithiation. Soft X-ray V L- and O K-edge measurements provide a detailed orbital-specific picture of changes in vanadium electronic structure upon discharge.

  8. Determination of zinc in serum, blood, and ultrafiltrate fluid from patients on hemofiltration by graphite furnace/atomic absorption spectroscopy or flow injection analysis/atomic absorption spectroscopy.

    de Blas, O J; Rodriguez, R S; Mendez, J H; Tomero, J A; Gomez, B de L; Gonzalez, S V

    1994-01-01

    Two methods were optimized for the determination of zinc in samples of blood, serum, and ultrafiltrate fluid from patients with chronic renal impairment undergoing hemofiltration. In the first procedure, after acid digestion of the samples, Zn in blood and serum is determined by a system coupled to flow injection analysis and atomic absorption spectroscopy. The method is rapid, automated, simple, needs small amounts of sample, and has acceptable analytical characteristics. The analytical characteristics obtained were as follows: determination range of method, 0.05-2.0 ppm of Zn; precision as coefficient of variation (CV), 5.3%; recovery, 95-105%; and detection limit (DL), 0.02 ppm. The second method is optimized for ultrafiltrate fluid because the sensitivity of the first procedure is not suitable for the levels of Zn (ppb or ng/mL) in these samples. The technique chosen was atomic absorption spectroscopy with electrothermal atomization in a graphite furnace. The analytical characteristics obtained were as follows: determination range of method, 0.3-2.0 ppb Zn; CV, 5.7%; recovery, 93-107%; and DL, 0.12 ppb. The methods were used to determine zinc in samples of blood, serum, and ultrafiltrate fluid from 5 patients with chronic renal impairment undergoing hemofiltration to discover whether there were significant differences in the zinc contents of blood, serum, and ultrafiltrate fluid after the hemofiltration process. An analysis of variance of the experimental data obtained from a randomly selected group of 5 patients showed that zinc concentrations in the ultrafiltrate fluid, venous blood, and venous serum do not vary during hemofiltration (p < 0.05), whereas in arterial blood and serum, the time factor has a significant effect.

  9. X-ray absorption spectroscopy investigations on radioactive matter using MARS beamline at SOLEIL synchrotron

    Llorens, Isabelle; Solari, Pier Lorenzo; Sitaud, Bruno [Synchrotron SOLEIL - l' Orme des Merisiers Saint Aubin, Gif-sur-Yvette (France); and others

    2014-07-01

    The MARS beamline at the SOLEIL synchrotron is dedicated to the characterization of radioactive material samples. One great advantage of the beamline is the possibility to characterize about 380 radionuclides by different X-ray techniques in the same place. This facility is unique in Europe. A wide energy range from around 3.5 keV to 36 keV K-edges from K to Cs, and L3 edges from Cd to Am and beyond can be used. The MARS beamline is optimized for X-ray absorption spectroscopy techniques (XANES/EXAFS), powder diffraction (XRD) but X-ray fluorescence (XRF) analysis, High Energy Resolution Fluorescence Detected-XAS (HERFD-XAS), X-ray Emission (XES) and μ-XAS/XRD are also possible. A description of the beamline as well as its performances are given in a first part. Then some scientific examples of XAS studies from users are presented which cover a wide variety of topics in radiochemistry and nuclear materials.

  10. Measurement of nickel, cobalt and chromium in toy make-up by atomic absorption spectroscopy.

    Corazza, Monica; Baldo, Federica; Pagnoni, Antonella; Miscioscia, Roberta; Virgili, Annarosa

    2009-01-01

    Cosmetics should not contain more than 5 ppm of nickel, chromium or cobalt and, in order to minimize the risk of sensitization in very sensitive subjects, the target amount should be as low as 1 ppm. However, there are no published reports on the presence of these metals in toy make-up. This study analysed 52 toy make-ups using atomic absorption spectroscopy. More than 5 ppm of nickel was present in 14/52 (26.9%) samples. Chromium exceeded 5 ppm in 28/52 (53.8%) samples, with values over 1000 ppm in 3 eye shadows. Cobalt was present in amounts over 5 ppm in 5/52 (9.6%) samples. Powdery toy make-up (eye shadows) had the highest levels of metals, and "creamy" toy make-up (lip gloss and lipsticks) the lowest. Toy make-ups are potentially sensitizing items, especially for atopic children, who have a damaged skin barrier that may favour penetration of allergens.

  11. Improved preparation of small biological samples for mercury analysis using cold vapor atomic absorption spectroscopy.

    Adair, B M; Cobb, G P

    1999-05-01

    Concentrations of mercury in biological samples collected for environmental studies are often less than 0.1 microgram/g. Low mercury concentrations and small organ sizes in many wildlife species (approximately 0.1 g) increase the difficulty of mercury determination at environmentally relevant concentrations. We have developed a digestion technique to extract mercury from small (0.1 g), biological samples at these relevant concentrations. Mean recoveries (+/- standard error) from validation trials of mercury fortified tissue samples using cold vapor atomic absorption spectroscopy for analysis ranged from 102 +/- 4.3% (2.5 micrograms/L, n = 15) to 108 +/- 1.4% (25 micrograms/L, n = 15). Recoveries of inorganic mercury were 99 +/- 5 (n = 19) for quality assurance samples analyzed during environmental evaluations conducted during a 24 month period. This technique can be used to determine total mercury concentrations of 60 ng Hg/g sample. Samples can be analyzed in standard laboratories in a short time, at minimal cost. The technique is versatile and can be used to determine mercury concentrations in several different matrices, limiting the time and expense of method development and validation.

  12. Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics.

    Merten, André; Tschritter, Jens; Platt, Ulrich

    2011-02-10

    We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.

  13. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  14. Speciation of Selenium in Stream Insects Using X-Ray Absorption Spectroscopy

    Andrahennadi, R.; Wayland, M.; Pickering, I.J.

    2009-05-28

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  15. Ultradast Absorption Spectroscopy of Aluminum Plasmas Created by LCLS using Betatron X-Ray Radiation

    Albert, Felicie [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-10-12

    This document summarizes the goals and accomplishments of a six month-long LDRD project, awarded through the LLNL director Early and Mid Career Recognition (EMCR) program. This project allowed us to support beamtime awarded at the Matter under Extreme Conditions (MEC) end station of the Linac Coherent Light Source (LCLS). The goal of the experiment was to heat metallic samples with the bright x-rays from the LCLS free electron laser. Then, we studied how they relaxed back to equilibrium by probing them with ultrafast x-ray absorption spectroscopy using laser-based betatron radiation. Our work enabled large collaborations between LLNL, SLAC, LBNL, and institutions in France and in the UK, while providing training to undergraduate and graduate students during the experiment. Following this LDRD project, the PI was awarded a 5-year DOE early career research grant to further develop applications of laser-driven x-ray sources for high energy density science experiments and warm dense matter states.

  16. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering [University of Saskatchewan, Saskatoon, SK (Canada). Department of Geological Sciences

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  17. Ultrafast Absorption Spectroscopy of Aluminum Plasmas Created by LCLS using Betatron X-Ray Radiation

    Albert, Felicie [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-10-12

    This document summarizes the goals and accomplishments of a six month-long LDRD project, awarded through the LLNL director Early and Mid Career Recognition (EMCR) program. This project allowed us to support beamtime awarded at the Matter under Extreme Conditions (MEC) end station of the Linac Coherent Light Source (LCLS). The goal of the experiment was to heat metallic samples with the bright x-rays from the LCLS free electron laser. Then, we studied how they relaxed back to equilibrium by probing them with ultrafast x-ray absorption spectroscopy using laser-based betatron radiation. Our work enabled large collaborations between LLNL, SLAC, LBNL, and institutions in France and in the UK, while providing training to undergraduate and graduate students during the experiment. Following this LDRD project, the PI was awarded a 5-year DOE early career research grant to further develop applications of laser-driven x-ray sources for high energy density science experiments and warm dense matter states.

  18. Use of X-ray absorption spectroscopy in the search for the best LIGO mirror coatings

    McGuire, Stephen C.

    2008-03-01

    The Laser Interferometer Gravitational-wave Observatory (LIGO) seeks to improve its sensitivity for gravity-wave detection by a factor of ten during its next phase of operation, Advanced LIGO. In order to achieve this goal it is necessary to design and fabricate test mass mirrors that help minimize the noise in the interferometers and in doing so maximize gravity-wave detection capability. In this talk we will present recent results from our program of X-ray absorption spectroscopy measurements to obtain detailed chemical composition and structure of titania (TiO2)-doped tantala (Ta2O5) multilayers fabricated via ion beam sputtering on SiO2 substrates. Our investigations focus on how the microscopic features of the coatings influence their macroscopic mechanical loss properties. Our goal is to obtain correlations between chemical impurities and/or dopants and the optical absorption and mechanical loss characteristics of these multilayer coatings. To examine our samples we use synchrotron-based X-ray absorption Spectroscopy (XAS) techniques including Extended X-ray Absorption Fine Structure (EXAFS), X-ray Absorption Near Edge Structure (XANES) and X-ray Fluorescence (XRF). We present chemical and structural data obtained at the titanium K-edge and tantalum LIII-edge as well as relative elemental distribution information (Ti/Ta, Fe/Ta, and Cr/Ta) obtained via XRF. Following a brief description of the LIGO experiment, our program of research in optical materials for use in advanced versions of the interferometer will be described.

  19. Coherent Light Photo-modification, Mass Transport Effect, and Surface Relief Formation in AsxS100-x Nanolayers: Absorption Edge, XPS, and Raman Spectroscopy Combined with Profilometry Study

    Kondrat, O.; Holomb, R.; Csik, A.; Takáts, V.; Veres, M.; Mitsa, V.

    2017-02-01

    As x S100- x ( x = 40, 45, 50) thin films top surface nanolayers affected by green (532 nm) diode laser illumination have been studied by high-resolution X-ray photoelectron spectroscopy, Raman spectroscopy, optical spectroscopy, and surface profilometry. It is shown that the composition of obtained films depends not only on the composition of the source material but as well on the composition of the vapor during the evaporation process. Near-bandgap laser light decreases both As-As and S-S homopolar bonds in films, obtained from thermal evaporation of the As40S60 and As50S50 glasses. Although As45S55 composition demonstrates increasing of As-As bonds despite to the partial disappearance of S-S bonds, for explanation of this phenomenon Raman investigations has also been performed. It is shown that As4S3 structural units (s.u.) responsible for the observed effect. Laser light induced surface topology of the As45S55 film has been recorded by 2D profilometer.

  20. Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in Novel Donor-Acceptor Core-Shell Nanostructures for Organic Photovoltaics

    Strain, Jacob; Jamhawi, Abdelqader; Abeywickrama, Thulitha M.; Loomis, Wendy; Rathnayake, Hemali; Liu, Jinjun

    2016-06-01

    Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

  1. Angle-tunable enhanced infrared reflection absorption spectroscopy via grating-coupled surface plasmon resonance.

    Petefish, Joseph W; Hillier, Andrew C

    2014-03-04

    Surface enhanced infrared absorption (SEIRA) spectroscopy is an attractive method for increasing the prominence of vibrational modes in infrared spectroscopy. To date, the majority of reports associated with SEIRA utilize localized surface plasmon resonance from metal nanoparticles to enhance electromagnetic fields in the region of analytes. Limited work has been performed using propagating surface plasmons as a method for SEIRA excitation. In this report, we demonstrate angle-tunable enhancement of vibrational stretching modes associated with a thin poly(methyl methacrylate) (PMMA) film that is coupled to a silver-coated diffraction grating. Gratings are fabricated using laser interference lithography to achieve precise surface periodicities, which can be used to generate surface plasmons that overlap with specific vibrational modes in the polymer film. Infrared reflection absorption spectra are presented for both bare silver and PMMA-coated silver gratings at a range of angles and polarization states. In addition, spectra were obtained with the grating direction oriented perpendicular and parallel to the infrared source in order to isolate plasmon enhancement effects. Optical simulations using the rigorous coupled-wave analysis method were used to identify the origin of the plasmon-induced enhancement. Angle-dependent absorption measurements achieved signal enhancements of more than 10-times the signal in the absence of the plasmon.

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

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

    2016-10-01

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

  3. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-07

    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.

  4. Measurements of Nighttime Nitrate Radical Concentrations in the Atmosphere by Long-Path Differential Optical Absorption Spectroscopy

    LI Suwen; LIU Wenqing; XIE Pinhua; LI Ang; QIN Min; DOU Ke

    2007-01-01

    The long-path differential optical absorption spectroscopy (LP-DOAS) technique was developed to measure nighttime atmospheric nitrate radical (NO3) concentrations. An optimized retrieval method, resulting in a small residual structure and low detection limits, was developed to retrieve NOs. The time series of the NO3 concentration were collected from 17 to 24 March, 2006, where a nighttime average value of 15.8 ppt was observed. The interfering factors and errors are also discussed. These results indicate that the DOAS technique provides an essential tool for the quantification of NO3 concentration and in the study of its effects upon nighttime chemistry.

  5. Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

    Ren, Yuan; Xing, Yaya; Ma, Guanxiong; Wang, Shiqi; An, Yukai, E-mail: ykan@tjut.edu.cn; Liu, Jiwen, E-mail: jwliu@tjut.edu.cn [Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Zhao, Xingliang [Beijing Aerospace Institute for Metrology and Measurement Technology, Beijing 100076 (China)

    2015-07-15

    The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cu atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.

  6. X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

    Dey, Abhishek; Hocking, Rosalie K.; /Stanford U., Chem. Dept.; Larsen, Peter; Borovik, Andrew S.; /Kansas U.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC,

    2006-09-27

    Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond.

  7. Investigation of neutral and ion dynamics in a HiPIMS plasma by tunable laser diode absorption spectroscopy (TDLAS)

    Preissing, Patrick; Hecimovic, Ante; von Keudell, Achim

    2016-09-01

    High power impulse magnetron sputtering (HiPIMS) discharges are known for complex plasma interactions, and complex temporal and spatial dynamics. Spatial and temporal dynamic of argon metastable (Arm), Ti atom (Ti0) and Ti ion (Ti+) density and temperature is studied by an extended tunable diode laser absorption spectroscopy setup (TDLAS) during a HiPIMS pulse. The TDLAS setup used a beam expander in combination with a 6 photo diode array to simultaneously measure spatial (resolution 5 mm) and time resolved absorption profiles of an Arm, Ti0 and Ti+ transition. This in combination with moving the magnetron in axial direction gives a complete 2D map of the density evolution. Temporal resolution of 400 ns was achieved by recording the photo diode signal on the National Instruments card. Final results allowed to investigate temporal evolution of the observed species in the volume between the target and the substrate.

  8. Anti-HepG-2 Cell Properties of Rare Earth Tungstosilicic Polyoxometalates Containing 5-Fluorouracil%The Study of Absorption Efficiency and Restoring Effects of Collagen and Ascorbic Acid on Aged Skin by Fluorescence and Reflection Spectroscopy

    LIU Xia; WANG Shuai-shuai; FENG Chang-gen

    2012-01-01

    Collagen is one of the main structural proteins in human dermis. The lack and atrophy of collagen induces the appearance of wrinkles and beginning of aging. L-ascorbic acid has significant effects on skin-whitening and anti-oxidation, which helps keep skin beautiful and healthy, respectively. With auto-fluorescence, the amount of collagen is in proportion to the strength of its fluorescence spectrum. Therefore, a new method is proposed to determine the content of collagen and the health of skin through the analysis of fluorescence and reflection spectra. Compared with conventional chemical analysis, this method needs less time, and is much more noninvasive. Solutions of different concentration of external collagen and L-ascorbic acid were applied on healthy, spotted and wrinkled skin in this study. By the time dependence of fluorescence and reflection spectra, the effects of skin absorption and restoration of collagen and L-ascorbic acid were derived, respectively. The experiment shows that the collagen or L-ascorbic acid solution of adequate concentration is best for skin absorption. Admixed with suitable concentration of L-ascorbic acid, the collagen solution was well absorbed and results in effect of smoothing wrinkles; the effect of L-ascorbic acid to clear up the spots was also demonstrated. By scientific explorations shown above, the restoration effects of cosmetic materials were validated, and people's confusion and myth about skincare products were avoided. Consequently, this study helps advance cosmetic industry.

  9. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

  10. Tunable Diode Laser Atomic Absorption Spectroscopy for Detection of Potassium under Optically Thick Conditions.

    Qu, Zhechao; Steinvall, Erik; Ghorbani, Ramin; Schmidt, Florian M

    2016-04-05

    Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer-Lambert's law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950-1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.

  11. Simulating systematic errors in X-ray absorption spectroscopy experiments: Sample and beam effects

    Curis, Emmanuel [Laboratoire de Biomathematiques, Faculte de Pharmacie, Universite Rene, Descartes (Paris V)-4, Avenue de l' Observatoire, 75006 Paris (France)]. E-mail: emmanuel.curis@univ-paris5.fr; Osan, Janos [KFKI Atomic Energy Research Institute (AEKI)-P.O. Box 49, H-1525 Budapest (Hungary); Falkenberg, Gerald [Hamburger Synchrotronstrahlungslabor (HASYLAB), Deutsches Elektronen-Synchrotron (DESY)-Notkestrasse 85, 22607 Hamburg (Germany); Benazeth, Simone [Laboratoire de Biomathematiques, Faculte de Pharmacie, Universite Rene, Descartes (Paris V)-4, Avenue de l' Observatoire, 75006 Paris (France); Laboratoire d' Utilisation du Rayonnement Electromagnetique (LURE)-Ba-hat timent 209D, Campus d' Orsay, 91406 Orsay (France); Toeroek, Szabina [KFKI Atomic Energy Research Institute (AEKI)-P.O. Box 49, H-1525 Budapest (Hungary)

    2005-07-15

    The article presents an analytical model to simulate experimental imperfections in the realization of an X-ray absorption spectroscopy experiment, performed in transmission or fluorescence mode. Distinction is made between sources of systematic errors on a time-scale basis, to select the more appropriate model for their handling. For short time-scale, statistical models are the most suited. For large time-scale, the model is developed for sample and beam imperfections: mainly sample inhomogeneity, sample self-absorption, beam achromaticity. The ability of this model to reproduce the effects of these imperfections is exemplified, and the model is validated on real samples. Various potential application fields of the model are then presented.

  12. The nature of arsenic in uranium mill tailings by X-ray absorption spectroscopy

    Cutler, J. N.; Chen, N.; Jiang, D. T.; Demopoulos, G. P.; Jia, Y.; Rowson, J. W.

    2003-05-01

    In order to understand the evolving world of environmental issues, the ability to characterize and predict the stability and bioavailability of heavy métal contaminants in mine waste is becoming increasingly more important. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies were used to characterize a series of synthetic and natural samples associated with mine tailings processing. XANES was shown to be excellent as a tool to rapidly differentiate oxidation states of arsenic within the samples. The EXAFS spectra provided information on the mineralogy of the precipitated raffinate and tailings and showed that these samples are composed of a mixture of amorphous ferric arsenates, adsorbed arsenates and a mixture of other poorly ordered arsenates.

  13. STRUCTURAL DETERMINATION OF TITANIUM-OXIDE NANOPARTICLES BY X-RAY ABSORPTION SPECTROSCOPY

    Z.Y.Wu; Y.N.Xie; Q.H.Zhang; L.Gao; Z.Z.Chen; J.Zhang; K.Ibrahim; M.I.Abbas; G.Li; Y.Tao; T.D.Hu; F.Q.Liu; H.J.Qian

    2002-01-01

    As a potential application of titanium-oxide nanoparticles, it is extremely importantto investigate a detailed picture of the surface and interior structural properties ofnanocrystalline materials, such as rutile and anatase with diameters 7.0 and 4.5nm,respectively. X-ray absorption spectroscopy has been used to identify the local Ti envi-ronment and related electronic structure. We combine the experimental results at theTi edge in both bulk and nano-crystals to determine the lattice distortion in terms ofdifferently characteristic preedge features and the variation in the multiple-scatteringregion of X-ray absorption near-edge structure (XANES) spectra. The relationshipbetween the transition peaks and the surface-to volume ratio is also discussed.

  14. Fourier-Transform Infrared Absorption Spectroscopy in Binary Hydrocarbon-Alcohol Single Droplet Evaporation

    Shane R. Daly

    2016-01-01

    Full Text Available Broadband absorption spectroscopy, by way of FTIR, was used to investigate the vapor cloud of a single millimeter sized liquid droplet suspended by a syringe as it evaporates at standard conditions. Single beam data were collected every 8 seconds resulting in a time-resolved record. Species concentrations were tracked using their resonant absorption peaks and correlated with a multidimensional numerical model. The numerical model combined a Gaussian beam transmission through a temporally changing spherical vapor cloud with radial concentration gradients, informed by the D2 law and interpreted using the Abel transform. There was fair agreement with temporal evaporation trends for single component runs. Multicomponent experiments of ethanol and isooctane showed synergistic blending effects and preferential evaporation of ethanol. Droplets were also suspended by a thermocouple to track the droplet temperature over time as they were subject to evaporative cooling. This work is the foundation of a basic technique for collecting useful data to inform a complex transport problem.

  15. Space Launch System Base Heating Test: Tunable Diode Laser Absorption Spectroscopy

    Parker, Ron; Carr, Zak; MacLean, Matthew; Dufrene, Aaron; Mehta, Manish

    2016-01-01

    This paper describes the Tunable Diode Laser Absorption Spectroscopy (TDLAS) measurement of several water transitions that were interrogated during a hot-fire testing of the Space Launch Systems (SLS) sub-scale vehicle installed in LENS II. The temperature of the recirculating gas flow over the base plate was found to increase with altitude and is consistent with CFD results. It was also observed that the gas above the base plate has significant velocity along the optical path of the sensor at the higher altitudes. The line-by-line analysis of the H2O absorption features must include the effects of the Doppler shift phenomena particularly at high altitude. The TDLAS experimental measurements and the analysis procedure which incorporates the velocity dependent flow will be described.

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

    Miaja-Avila, L; O'Neil, G C; Uhlig, J; Cromer, C L; Dowell, M L; Jimenez, R; Hoover, A S; Silverman, K L; Ullom, J N

    2015-03-01

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

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

    L. Miaja-Avila

    2015-03-01

    Full Text Available We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  18. The determination of aluminum, copper, iron, and lead in glycol formulations by atomic absorption spectroscopy

    1977-01-01

    Initial screening tests and the results obtained in developing procedures to determine Al, Cu, Fe, and Pb in glycol formulations are described. Atomic absorption completion was selected for Cu, Fe and Pb, and after comparison with emission spectroscopy, was selected for Al also. Before completion, carbon, iron, and lead are extracted with diethyl dithio carbamate (DDC) into methyl isobutyl ketone (MIBK). Aluminum was also extracted into MIBK using 8-hydroxyquinoline as a chelating agent. As little as 0.02 mg/l carbon and 0.06 mg/l lead or iron may be determined in glycol formulations. As little as 0.3 mg/l aluminum may be determined.

  19. [Measurement of trace elements in blood serum by atomic absorption spectroscopy with electrothermal atomization].

    Rogul'skiĭ, Iu V; Danil'chenko, S N; Lushpa, A P; Sukhodub, L F

    1997-09-01

    Describes a method for measuring trace elements Cr, Mn, Co, Fe, Cu, Zn, and Mo in the blood serum using non-flame atomization (KAC 120.1 complex). Optimal conditions for preparing the samples were defined, temperature regimens for analysis of each element selected, and original software permitting automated assays created. The method permits analysis making use of the minimal samples: 0.1 ml per 10 parallel measurements, which is 100 times less than needed for atomic absorption spectroscopy with flame atomization of liquid samples. Metrological characteristics of the method are assessed.

  20. Excited state absorption spectroscopy of ZBLAN:Er3+ glass - Experiment and simulation

    Piatkowski, D.; Wisniewski, K.; Rozanski, M.; Koepke, Cz.

    2009-08-01

    We present the excited state absorption (ESA) spectroscopy of ZBLAN:Er3+ glass. The experimental spectra were measured in broad spectral range (500-1800 nm) by the CW pump-probe technique. Judd-Ofelt (JO) approach was employed to interpret the results and to simulate the ESA spectra which were successfully confronted with the experiment. We also propose a systematic approach for prediction of various types of up-conversion mechanisms such as ESA up-conversion and photon avalanche (PA). Careful investigations were made to indicate possible up-conversion excitation channels in a wide spectral range, from 400 nm up to 2 μm.

  1. Multiplexed detection of xylene and trichloroethylene in water by photonic crystal absorption spectroscopy.

    Lai, Wei-Cheng; Chakravarty, Swapnajit; Zou, Yi; Chen, Ray T

    2013-10-01

    We experimentally demonstrate simultaneous selective detection of xylene and trichloroethylene (TCE) using multiplexed photonic crystal waveguides (PCWs) by near-infrared optical absorption spectroscopy on a chip. Based on the slow light effect of photonic crystal structure, the sensitivity of our device is enhanced to 1 ppb (v/v) for xylene and 10 ppb (v/v) for TCE in water. Multiplexing is enabled by multimode interference power splitters and Y-combiners that integrate multiple PCWs on a silicon chip in a silicon-on-insulator platform.

  2. Glucose sensing by waveguide-based absorption spectroscopy on a silicon chip

    2014-01-01

    In this work, we demonstrate in vitro detection of glucose by means of a lab-on-chip absorption spectroscopy approach. This optical method allows label-free and specific detection of glucose. We show glucose detection in aqueous glucose solutions in the clinically relevant concentration range with a silicon-based optofluidic chip. The sample interface is a spiral-shaped rib waveguide integrated on a silicon-on-insulator (SOI) photonic chip. This SOI chip is combined with micro-fluidics in pol...

  3. Determination of heavy metals in solid emission and immission samples using atomic absorption spectroscopy

    Fara, M.; Novak, F. [EGU Prague, PLC, Bichovice, Prague (Czechoslovakia)

    1995-12-01

    Both flame and electrothermal methods of atomic absorption spectroscopy (AAS) have been applied to the determination of Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, TI, Se, V and Zn in emission and emission (deposition) samples decomposed in open PTFE test-tubes by individual fuming-off hydrofluoric, perchloroic and nitric acid. An alternative hydride technique was also used for As and Se determination and Hg was determined using a self-contained AAS analyzer. A graphite platform proved good to overcome non-spectral interferences in AAS-ETA. Methods developed were verified by reference materials (inc. NBS 1633a).

  4. Investigation of Diode Pumped Alkali Laser Atmospheric Transmission Using Tunable Diode Laser Absorption Spectroscopy

    2012-09-01

    House Appropriations hearing on May 20th, 2010 where Robert Gates, then U.S. Secretary of Defense, said the following in answer to a question from Rep...Henry, B. P. Wert, T. Gilpin , and J. R. Drummond. “Tunable diode laser absorption spectrometer for ground-based measurements of formaldehyde”. Journal...spectroscopy (TDLAS) at 1.37 µm”. Applied Physics B: Lasers and Optics, 92(3):393–401, 2008. 43. Kormann, Robert , Horst Fischer, and Frank G. Wienhold

  5. Two attosecond pulse transient absorption spectroscopy and extraction of the instantaneous AC Stark shift in helium

    Bækhøj, Jens E.; Bojer Madsen, Lars

    2016-07-01

    In two attosecond pulse absorption spectroscopy (TAPAS) the use of two attosecond XUV pulses allows the extraction of atomic and molecular quantum mechanical dipole phases from spectroscopic measurements. TAPAS relies on interference between processes that individually only include a single XUV photon, and therefore does not rely on high intensity attosecond pulses. To show the usefulness and limitations of the TAPAS method we investigate its capability of capturing the instantaneous AC Stark shift induced by a midinfrared 3200 nm pulse in the | 1{{s}}2{{p}}> state of helium.

  6. Behaviors of harmonic signals in wavelength-modulated spectroscopy under high absorption strength

    Yuntao Wang; Haiwen Cai; Jianxin Geng; Zhengqing Pan; Dijun Chen; Zujie Fang

    2007-01-01

    @@ Behaviors of harmonic signals in wavelength modulation spectroscopy (WMS) for gas detection with Lorentzian line under high absorption strength are investigated. Approximate analytic expressions of the second, fourth, and sixth harmonics on the strength are presented in concise forms. Simulations show that the expressions are in agreement with the Fourier expansion by numerical integration. It is expected theoretically and experimentally in a WMS system for methane detection that there are not only a maximum, but also a null point in the harmonics versus strength relations, which should be of practical importance in methane sensing applications.

  7. A quality control technique based on UV-VIS absorption spectroscopy for tequila distillery factories

    Barbosa Garcia, O.; Ramos Ortiz, G.; Maldonado, J. L.; Pichardo Molina, J.; Meneses Nava, M. A.; Landgrave, Enrique; Cervantes, M. J.

    2006-02-01

    A low cost technique based on the UV-VIS absorption spectroscopy is presented for the quality control of the spirit drink known as tequila. It is shown that such spectra offer enough information to discriminate a given spirit drink from a group of bottled commercial tequilas. The technique was applied to white tequilas. Contrary to the reference analytic methods, such as chromatography, for this technique neither special personal training nor sophisticated instrumentations is required. By using hand-held instrumentation this technique can be applied in situ during the production process.

  8. IDENTIFICATION OF ADULTERANT AND ALCOHOL ROUTE IN BIODIESEL USING MID-INFRARED ABSORPTION SPECTROSCOPY

    Maryleide Ventura da Silva

    2014-01-01

    Full Text Available Mid-infrared absorption spectroscopy was used to analyze soybean oil, ethylic and methylic soybean biodiesel, and blends prepared with soybean oil mixed with biodiesel, in order to evaluate this method as an alternative to assess oil as impurities or adulterant in biodiesel. We also aimed to determine whether the biodiesel was prepared by the ethyl or methyl routes, by inspecting the infrared spectra. The C-O functional groups between 1100 and 1200 cm-1 are different for oil and biodiesel, which allows them to be used to distinguish impurities (residual oil in biofuel. The peak C-O-C at 1017 cm-1 is characteristic for methylic biodiesel, and the peak O-C-C at 1035 cm-1 for ethylic biodiesel. These vibrational modes can therefore be used to indicate the route used to prepare the biofuel. Results indicated that infrared spectroscopy is appropriate for monitoring the quality of biofuel for commercial sale.

  9. Microscale X-ray Absorption Spectroscopy on the GSECARS Sector 13 at the APS

    Stephen-Sutto

    2000-01-01

    GeoSoilEnviroCARS (GSECARS) is a national user facility for frontier research in the earth sciences using synchrotrons radiation at the Advanced Photon Source, Argonne National Laboratory. GSECARS provides earth scientists with access to the high-brilliance hard x-rays from this third-generation synchrotrons light source. The research conducted at this facility will advance our knowledge of the composition, structure and properties of earth materials, the processes they control and the processes that produce them. All principal synchrotron-based analytical techniques in demand by earth scientists are being brought to bear on earth science problems: (1) high-pressure/high-temperature crystallography and spectroscopy using the diamond anvil cell; (2) high-pressure/high-temperature crystallography using the large-volume press; (3) powder, single crystal and interface diffraction; (4) x-ray absorption fine structure (XAFS) spectroscopy; (5) x-ray fluorescence microprobe analysis and microspectroscopy; and (6) mic...

  10. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy

    Blättermann, Alexander; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2016-01-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  11. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy.

    Blättermann, Alexander; Ott, Christian; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2015-08-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field-driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  12. An investigation of the chromium oxidation state of a monoanionic chromium tris(catecholate) complex by X-ray absorption and EPR spectroscopies

    Pattison, D I; Levina, A; Davies, Michael Jonathan;

    2001-01-01

    The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The p...

  13. Polarized X-ray absorption spectroscopy of single-crystal Mn(V) complexes relevant to the oxygen-evolving complex of photosystem II

    Yano, Junko; Robblee, John; Pushkar, Yulia

    2007-01-01

    structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the manganese...

  14. A Complete Overhaul of the Electron Energy-Loss Spectroscopy and X-Ray Absorption Spectroscopy Database: eelsdb.eu.

    Ewels, Philip; Sikora, Thierry; Serin, Virginie; Ewels, Chris P; Lajaunie, Luc

    2016-06-01

    The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors' original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra.

  15. X-ray absorption studies of battery materials

    McBreen, J.

    1996-10-01

    X-ray absorption spectroscopy (XAS) is ideal for {ital in}{ital situ} studies of battery materials because both the probe and signal are penetrating x rays. The advantage of XAS being element specific permits investigation of the environment of a constituent element in a composite material. This makes it very powerful for studying electrode additives and corrosion of individual components of complex metal hydride alloys. The near edge part of the spectrum (XANES) provides information on oxidation state and site symmetry of the excited atom. This is particularly useful in study of corrosion and oxidation changes in cathode materials during charge/discharge cycle. Extended fine structure (EXAFS) gives structural information. Thus the technique provides both chemical and structural information. Since XAS probes only short range order, it can be applied to study of amorphous electrode materials and electrolytes. This paper discusses advantages and limitations of the method, as well as some experimental aspects.

  16. Structural changes in a polyelectrolyte multilayer assembly investigated by reflection absorption infrared spectroscopy and sum frequency generation spectroscopy.

    Kett, Peter J N; Casford, Michael T L; Yang, Amanda Y; Lane, Thomas J; Johal, Malkiat S; Davies, Paul B

    2009-02-12

    The structure of polyelectrolyte multilayer films adsorbed onto either a per-protonated or per-deuterated 11-mercaptoundecanoic acid (h-MUA/d-MUA) self assembled monolayer (SAM) on gold was investigated in air using two surface vibrational spectroscopy techniques, namely, reflection absorption infrared spectroscopy (RAIRS) and sum frequency generation (SFG) spectroscopy. Determination of film masses and dissipation values were made using a quartz crystal microbalance with dissipation monitoring (QCM-D). The films, containing alternating layers of the polyanion poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and the polycation poly(ethylenimine) (PEI) built on the MUA SAM, were formed using the layer-by-layer electrostatic self-assembly method. The SFG spectrum of the SAM itself comprised strong methylene resonances, indicating the presence of gauche defects in the alkyl chains of the acid. The RAIRS spectrum of the SAM also contained strong methylene bands, indicating a degree of orientation of the methylene groups parallel to the surface normal. Changes in the SFG and RAIRS spectra when a PEI layer was adsorbed on the MUA monolayer showed that the expected electrostatic interaction between the polymer and the SAM, probably involving interpenetration of the PEI into the MUA monolayer, caused a straightening of the alkyl chains of the MUA and, consequently, a decrease in the number of gauche defects. When a layer of PAZO was subsequently deposited on the MUA/PEI film, further spectral changes occurred that can be explained by the formation of a complex PEI/PAZO interpenetrated layer. A per-deuterated MUA SAM was used to determine the relative contributions from the adsorbed polyelectrolytes and the MUA monolayer to the RAIRS and SFG spectra. Spectroscopic and adsorbed mass measurements combined showed that as further bilayers were constructed the interpenetration of PAZO into preadsorbed PEI layers was repeated, up to

  17. Study on Performance and Mechanism of Oil Absorption Materials

    韩梅; 吴兵; 李发生; 何绪文; 谷庆宝

    2001-01-01

    Both the commonly used and the PHBV based oil absorption materials were studied and the absorption mechanism was analyzed. The results show that the oil pick-up ratios and the absorption rates of molded PHBV are almost the same as that of oil absorption polypropylene felt. In addition, the oil-keeping ability of molded PHBV is superior to the latter. So the PHBV is a valuable and bio-degradable oil absorption material.

  18. Actinides in molecules: exotic properties probed by X-ray Absorption Spectroscopy

    Den Auwer, C.; Moisy, P.; Guilbaud, P.; Guillaumont, D.; Simoni, E.; Conradson, S.D

    2004-07-01

    Dealing with actinide elements in molecular chemistry may result in particularly attractive and exotic physico-chemical properties. In solution, one of the spectroscopic tools able to selectively probe the structural or electronic properties of these molecules is the X-ray absorption process. Different aspects of absorption edge or EXAFS analysis related to actinide studies are presented, including phenomenological and semi-quantitative approaches. (authors)

  19. Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

    Karhu, J.; Nauta, J.; Vainio, M.; Metsälä, M.; Hoekstra, S.; Halonen, L.

    2016-06-01

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, ν 1 + ν 2 + ν 3 + ν4 1 + ν5 - 1 in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) cm-1, the rotational parameter B was 1.162 222(37) cm-1, and the quartic centrifugal distortion parameter D was 3.998(62) × 10-6 cm-1, where the numbers in the parenthesis are one-standard errors in the least significant digits.

  20. Total Absorption Spectroscopy of the 137Xe, 137I, and 92Rb β-Decays

    Rasco, B. C.; Fijałkowska, A.; Karny, M.; Rykaczewski, K. P.; Wolińska-Cichocka, M.; Goetz, K. C.; Grzywacz, R. K.; Gross, C. J.; Miernik, K.; Stracener, D.

    2015-10-01

    The NaI(Tl) based Modular Total Absorption Spectrometer (MTAS) was constructed to measure improved β-decay feeding patterns from neutron-rich nuclei. It is difficult to measure β-decay feeding intensities with high precision γ-ray measurements due to the low efficiency of high precision detectors. There are several important applications of improved measurements of β-decay feeding patterns by total absorption spectroscopy; improve understanding of elemental abundances in the universe, help with stockpile stewardship, contribute to understanding of underlying nuclear structure, and improve β-decay feeding measurements to calculate accurately the νe spectra needed to evaluate precisely reactor neutrino measurements. We present β-decay feeding results for two ``priority one'' measurements, 137Xe and 137I, and for 92Rb, which is a large individual contributor to the νe uncertainty of the reactor anomaly. In addition to β- γ decays, 137I has a β-neutron decay channel which is measurable in MTAS. We will demonstrate techniques for analyzing MTAS γ-decay data. We will also describe β and neutron spectroscopy in MTAS. This work was supported by the US DOE by Award No. DE-FG02- 96ER40978 and by US DOE, Office of Nuclear Physics.

  1. Novel focal point multipass cell for absorption spectroscopy on small sized atmospheric pressure plasmas.

    Winter, Jörn; Hänel, Mattis; Reuter, Stephan

    2016-04-01

    A novel focal point multipass cell (FPMPC) was developed, in which all laser beams propagate through a common focal point. It is exclusively constructed from standard optical elements. Main functional elements are two 90(∘) off-axis parabolic mirrors and two retroreflectors. Up to 17 laser passes are demonstrated with a near-infrared laser beam. The number of laser passes is precisely adjustable by changing the retroreflector distance. At the focal point beams are constricted to fit through an aperture of 0.8 mm. This is shown for 11 beam passes. Moreover, the fast temporal response of the cell permits investigation of transient processes with frequencies up to 10 MHz. In order to demonstrate the applicability of the FPMPC for atmospheric pressure plasma jets, laser absorption spectroscopy on the lowest excited argon state (1s5) was performed on a 1 MHz argon atmospheric pressure plasma jet. From the obtained optical depth profiles, the signal-to-noise ratio was deduced. It is shown that an elevation of the laser pass number results in an proportional increase of the signal-to-noise ratio making the FPMPC an appropriate tool for absorption spectroscopy on plasmas of small dimensions.

  2. Glucose sensing by waveguide-based absorption spectroscopy on a silicon chip.

    Ryckeboer, E; Bockstaele, R; Vanslembrouck, M; Baets, R

    2014-05-01

    In this work, we demonstrate in vitro detection of glucose by means of a lab-on-chip absorption spectroscopy approach. This optical method allows label-free and specific detection of glucose. We show glucose detection in aqueous glucose solutions in the clinically relevant concentration range with a silicon-based optofluidic chip. The sample interface is a spiral-shaped rib waveguide integrated on a silicon-on-insulator (SOI) photonic chip. This SOI chip is combined with micro-fluidics in poly(dimethylsiloxane) (PDMS). We apply aqueous glucose solutions with different concentrations and monitor continuously how the transmission spectrum changes due to glucose. Based on these measurements, we derived a linear regression model, to relate the measured glucose spectra with concentration with an error-of-fitting of only 1.14 mM. This paper explains the challenges involved and discusses the optimal configuration for on-chip evanescent absorption spectroscopy. In addition, the prospects for using this sensor for glucose detection in complex physiological media (e.g. serum) is briefly discussed.

  3. Novel focal point multipass cell for absorption spectroscopy on small sized atmospheric pressure plasmas

    Winter, Jörn; Hänel, Mattis; Reuter, Stephan

    2016-04-01

    A novel focal point multipass cell (FPMPC) was developed, in which all laser beams propagate through a common focal point. It is exclusively constructed from standard optical elements. Main functional elements are two 90∘ off-axis parabolic mirrors and two retroreflectors. Up to 17 laser passes are demonstrated with a near-infrared laser beam. The number of laser passes is precisely adjustable by changing the retroreflector distance. At the focal point beams are constricted to fit through an aperture of 0.8 mm. This is shown for 11 beam passes. Moreover, the fast temporal response of the cell permits investigation of transient processes with frequencies up to 10 MHz. In order to demonstrate the applicability of the FPMPC for atmospheric pressure plasma jets, laser absorption spectroscopy on the lowest excited argon state (1s5) was performed on a 1 MHz argon atmospheric pressure plasma jet. From the obtained optical depth profiles, the signal-to-noise ratio was deduced. It is shown that an elevation of the laser pass number results in an proportional increase of the signal-to-noise ratio making the FPMPC an appropriate tool for absorption spectroscopy on plasmas of small dimensions.

  4. UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 1: basic principles and properties of tyrosine chromophore.

    Antosiewicz, Jan M; Shugar, David

    Spectroscopic properties of tyrosine residues may be employed in structural studies of proteins. Here we discuss several different types of UV-Vis spectroscopy, like normal, difference and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, and corresponding optical properties of the tyrosine chromophore, phenol, which are used to study protein structure.

  5. HCl yield and chemical kinetics study of the reaction of Cl atoms with CH3I at the 298K temperature using the infra-red tunable diode laser absorption spectroscopy.

    Sharma, R C; Blitz, M; Wada, R; Seakins, P W

    2014-07-15

    Pulsed ArF excimer laser (193 nm)-CW infrared (IR) tunable diode laser Herriott type absorption spectroscopic technique has been made for the detection of product hydrochloric acid HCl. Absorption spectroscopic technique is used in the reaction chlorine atoms with methyl iodide (Cl+CH3I) to the study of kinetics on reaction Cl+CH3I and the yield of (HCl). The reaction of Cl+CH3I has been studied with the support of the reaction Cl+C4H10 (100% HCl) at temperature 298 K. In the reaction Cl+CH3I, the total pressure of He between 20 and 125 Torr at the constant concentration of [CH3I] 7.0×10(14) molecule cm(-3). In the present work, we estimated adduct formation is very important in the reaction Cl+CH3I and reversible processes as well and CH3I molecule photo-dissociated in the methyl [CH3] radical. The secondary chemistry has been studied as CH3+CH3ICl = product, and CH3I+CH3ICl = product2. The system has been modeled theoretically for secondary chemistry in the present work. The calculated and experimentally HCl yield nearly 65% at the concentration 1.00×10(14) molecule cm(-3) of [CH3I] and 24% at the concentration 4.0×10(15) molecule cm(-3) of [CH3I], at constant concentration 4.85×10(12) molecule cm(-3) of [CH3], and at 7.3×10(12) molecule cm(-3) of [Cl]. The pressure dependent also studied product of HCl at the constant [CH3], [Cl] and [CH3I]. The experimental results are also very good matching with the modelling work at the reaction CH3+CH3ICl = product (k = (2.75±0.35)×10(-10) s(-1)) and CH3I+CH3ICl = product2 (k = 1.90±0.15)×10(-12) s(-1). The rate coefficients of the reaction CH3+CH3ICl and CH3I+CH3ICl has been made in the present work. The experimental results has been studied by two method (1) phase locked and (2) burst mode.

  6. A New Flexible Monochromator Setup for Quick Scanning X-ray Absorption Spectroscopy

    Stotzel, J.; Lutzenkirchen-Hecht, D; Frahm, R

    2010-01-01

    A new monochromator setup for quick scanning x-ray absorption spectroscopy in the subsecond time regime is presented. Novel driving mechanics allow changing the energy range of the acquired spectra by remote control during data acquisition for the first time, thus dramatically increasing the flexibility and convenience of this method. Completely new experiments are feasible due to the fact that time resolution, edge energy, and energy range of the acquired spectra can be changed continuously within seconds without breaking the vacuum of the monochromator vessel and even without interrupting the measurements. The advanced mechanics are explained in detail and the performance is characterized with x-ray absorption spectra of pure metal foils. The energy scale was determined by a fast and accurate angular encoder system measuring the Bragg angle of the monochromator crystal with subarcsecond resolution. The Bragg angle range covered by the oscillating crystal can currently be changed from 0{sup o} to 3.0{sup o} within 20 s, while the mechanics are capable to move with frequencies of up to ca. 35 Hz, leading to ca. 14 ms/spectrum time resolution. A new software package allows performing programmed scan sequences, which enable the user to measure stepwise with alternating parameters in predefined time segments. Thus, e.g., switching between edges scanned with the same energy range is possible within one in situ experiment, while also the time resolution can be varied simultaneously. This progress makes the new system extremely user friendly and efficient to use for time resolved x-ray absorption spectroscopy at synchrotron radiation beamlines.

  7. A new flexible monochromator setup for quick scanning x-ray absorption spectroscopy

    Stoetzel, J.; Luetzenkirchen-Hecht, D.; Frahm, R. [Fachbereich C, Physik, Bergische Universitaet Wuppertal, Gaussstr. 20, 42097 Wuppertal (Germany)

    2010-07-15

    A new monochromator setup for quick scanning x-ray absorption spectroscopy in the subsecond time regime is presented. Novel driving mechanics allow changing the energy range of the acquired spectra by remote control during data acquisition for the first time, thus dramatically increasing the flexibility and convenience of this method. Completely new experiments are feasible due to the fact that time resolution, edge energy, and energy range of the acquired spectra can be changed continuously within seconds without breaking the vacuum of the monochromator vessel and even without interrupting the measurements. The advanced mechanics are explained in detail and the performance is characterized with x-ray absorption spectra of pure metal foils. The energy scale was determined by a fast and accurate angular encoder system measuring the Bragg angle of the monochromator crystal with subarcsecond resolution. The Bragg angle range covered by the oscillating crystal can currently be changed from 0 deg. to 3.0 deg. within 20 s, while the mechanics are capable to move with frequencies of up to ca. 35 Hz, leading to ca. 14 ms/spectrum time resolution. A new software package allows performing programmed scan sequences, which enable the user to measure stepwise with alternating parameters in predefined time segments. Thus, e.g., switching between edges scanned with the same energy range is possible within one in situ experiment, while also the time resolution can be varied simultaneously. This progress makes the new system extremely user friendly and efficient to use for time resolved x-ray absorption spectroscopy at synchrotron radiation beamlines.

  8. Impact of atmospheric state uncertainties on retrieved XCO2 columns from laser differential absorption spectroscopy measurements

    Zaccheo, T. Scott; Pernini, Timothy; Snell, Hilary E.; Browell, Edward V.

    2014-01-01

    This work assesses the impact of uncertainties in atmospheric state knowledge on retrievals of carbon dioxide column amounts (XCO2) from laser differential absorption spectroscopy (LAS) measurements. LAS estimates of XCO2 columns are normally derived not only from differential absorption observations but also from measured or prior knowledge of atmospheric state that includes temperature, moisture, and pressure along the viewing path. In the case of global space-based monitoring systems, it is often difficult if not impossible to provide collocated in situ measurements of atmospheric state for all observations, so retrievals often rely on collocated remote-sensed data or values derived from numerical weather prediction (NWP) models to describe the atmospheric state. A radiative transfer-based simulation framework, combined with representative global upper-air observations and matched NWP profiles, was used to assess the impact of model differences on estimates of column CO2 and O2 concentrations. These analyses focus on characterizing these errors for LAS measurements of CO2 in the 1.57-μm region and of O2 in the 1.27-μm region. The results provide a set of signal-to-noise metrics that characterize the errors in retrieved values associated with uncertainties in atmospheric state and provide a method for selecting optimal differential absorption line pairs to minimize the impact of these noise terms.

  9. Broadband fitting approach for the application of supercontinuum broadband laser absorption spectroscopy to combustion environments

    Göran Blume, Niels; Ebert, Volker; Dreizler, Andreas; Wagner, Steven

    2016-01-01

    In this work, a novel broadband fitting approach for quantitative in-flame measurements using supercontinuum broadband laser absorption spectroscopy (SCLAS) is presented. The application and verification of this approach in an atmospheric, laminar, non-premixed CH4/air flame (Wolfhard-Parker burner, WHP) is discussed. The developed fitting scheme allows for an automatic recognition and fitting of a B-spline curve reference intensity for SCLAS broadband measurements while automatically removing the influence of absorption peaks. This approach improves the fitting residual locally (in between absorption lines) and globally by 23% and 13% respectively, while improving the in-flame SNR by a factor of 2. Additionally, the approach inherently improves the time-wavelength-correlation based on recorded in-flame measurements itself in combination with a theoretical spectrum of the analyte. These improvements have allowed for the recording of complete spatially resolved methane concentration profiles in the WHP burner. Comparison of the measured absolute mole fraction profile for methane with previously measured reference data shows excellent agreement in position, shape and absolute values. These improvements are a prerequisite for the application of SCLAS in high-pressure combustion systems.

  10. The amorphous Zn biomineralization at Naracauli stream, Sardinia: electron microscopy and X-ray absorption spectroscopy.

    Medas, D; Lattanzi, P; Podda, F; Meneghini, C; Trapananti, A; Sprocati, A; Casu, M A; Musu, E; De Giudici, G

    2014-01-01

    An amorphous Zn biomineralization ("white mud"), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.

  11. Synthesis in fluoride medium and characterisation of Montmorillonite type Photoelasticity. Structural study by X-ray Absorption and nuclear magnetic resonance spectroscopies; Synthese en milieu fluore et caracterisation de phyllosilicates de type montmorillonite. etude structurale par spectroscopies d'absorption des rayons x et de resonance magnetique nucleaire

    Reinholdt, M.

    2001-12-15

    The aim of this work is to synthesize and characterise montmorillonite type phyllosilicates and to study the distribution of the metal elements in the structure. First, generalities about phyllosilicates are introduced. A particular attention is given to (2:1) di-octahedral phyllosilicates and especially to montmorillonite. The different methods of the synthesis of this mineral are reviewed. The method of hydrothermal synthesis in fluoride medium and the techniques used to characterize the materials (XRD, TGA-DTA, chemical analyses) are then described. The descriptions of solid state NMR and EXAFS are particularly developed. Next, a systematic study of the synthetic products is realised for two systems MO-Al{sub 2}O{sub 3}-SiO{sub 2} (M = Mg or Zn). The compositions of hydrogel are based on a theoretical formula of montmorillonite: Na{sub 2x}[Al{sub 2(1-x)}M{sub 2x}-vacancy]Si{sub 4}O{sub 10}OH{sub 2} (x represents the octahedral layer charge). A montmorillonite type phyllosilicate is obtained for 0.10 {<=} x {<=} 0.25 in the MgO-Al{sub 2}O{sub 3}-SiO{sub 2} system and for x = 0.10 in the ZnO-Al{sub 2}O{sub 3}-SiO{sub 2} system. Besides the Mg/Al substitutions in the octahedral sheet, Al/Si substitutions in the tetrahedral sheet are observed by {sup 29}Si and {sup 27}Al NMR. The {sup 19}F NMR shows a clustering of the octahedral elements in (Mg)phyllosilicate. Then, the parameters of the synthesis of (Mg)phyllosilicate are introduced. Kaolinite is observed as an intermediary phase during the crystallisation. The optimal pH is found between 5.0 and 5.5. The presence of a little amount of F- is necessary (0.05 {<=} F/SiO{sub 2} {<=} 0.10). Tetrahedral substitutions are fewer with the use of Na{sup +} as compensating cation. Finally, Zn and Mg K-edges EXAFS show a distortion of the layer and a clustering of the octahedral elements for the (Zn)phyllosilicate. A quantitative {sup 27}Al MAS-NMR method is elaborated which allows to determine both total amount of aluminium

  12. High-Resolution X-ray Spectroscopy of the Interstellar Medium II: Neon and Iron Absorption Edges

    Juett, A M; Chakraborty, D; Gorczyca, T W; Juett, Adrienne M.; Schulz, Norbert S.; Chakrabarty, Deepto; Gorczyca, Thomas W.

    2006-01-01

    We present high-resolution spectroscopy of the neon K-shell and iron L-shell interstellar absorption edges in nine X-ray binaries using the High Energy Transmission Grating Spectrometer (HETGS) onboard the Chandra X-ray Observatory. We found that the iron absorption is well fit by an experimental determination of the cross-section for metallic iron, although with a slight wavelength shift of ~20 mA. The neon edge region is best fit by a model that includes the neutral neon edge and three Gaussian absorption lines. We identify these lines as due to the 1s-2p transitions from Ne II, Ne III, and Ne IX. As we found in our oxygen edge study, the theoretical predictions for neutral and low-ionization lines all require shifts of ~20 mA to match our data. Combined with our earlier oxygen edge study, we find that a best fit O/Ne ratio of 5.4+/-1.6, consistent with standard interstellar abundances. Our best fit Fe/Ne ratio of 0.20+/-0.03 is significantly lower than the interstellar value. We attribute this difference t...

  13. Cavity ring-down study of the visible absorption spectrum of the phenyl radical and kinetics of its reactions with Cl, Br, Cl-2, and O-2

    Tonokura, K; Norikane, Y; Koshi, M;

    2002-01-01

    Cavity ring-down spectroscopy coupled with pulsed laser photolysis was used to study the visible absorption spectrum (490-535 nm, B-2(1)......Cavity ring-down spectroscopy coupled with pulsed laser photolysis was used to study the visible absorption spectrum (490-535 nm, B-2(1)...

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

    Gann, Eliot; McNeill, Christopher R., E-mail: christopher.mcneill@monash.edu [Department of Materials Engineering, Monash University, Wellington Road, Clayton, Victoria 3800 (Australia); Szumilo, Monika; Sirringhaus, Henning [Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Sommer, Michael [Institute of Macromolecular Chemistry, University of Freiburg, Stefan-Meier-Str. 31, 79104 Freiburg (Germany); Maniam, Subashani; Langford, Steven J. [School of Chemistry, Monash University, Wellington Road, Clayton, Victoria 3800 (Australia); Thomsen, Lars [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2014-04-28

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

  15. Absorption spectroscopy characterization measurements of a laser-produced Na atomic beam

    Ching, C.H.; Bailey, J.E.; Lake, P.W.; Filuk, A.B.; Adams, R.G.; McKenney, J.

    1996-06-01

    This work describes a pulsed Na atomic beam source developed for spectroscopic diagnosis of a high-power ion diode on the Particle Beam Fusion Accelerator II. The goal is to produce a {approximately} 10{sup 12}-cm{sup {minus}3}-density Na atomic beam that can be injected into the diode acceleration gap to measure electric and magnetic fields from the Stark and Zeeman effects through laser-induced-fluorescence or absorption spectroscopy. A {approximately} 10 ns fwhm, 1.06 {micro}m, 0.6 J/cm{sup 2} laser incident through a glass slide heats a Na-bearing thin film, creating a plasma that generates a sodium vapor plume. A {approximately} 1 {micro}sec fwhm dye laser beam tuned to 5,890 {angstrom} is used for absorption measurement of the Na I resonant doublet by viewing parallel to the film surface. The dye laser light is coupled through a fiber to a spectrograph with a time-integrated CCD camera. A two-dimensional mapping of the Na vapor density is obtained through absorption measurements at different spatial locations. Time-of-flight and Doppler broadening of the absorption with {approximately} 0.1 {angstrom} spectral resolution indicate that the Na neutral vapor temperature is about 0.5 to 2 eV. Laser-induced-fluorescence from {approximately} 1 {times} 10{sup 12}-cm{sup {minus}3} Na I 3s-3p lines observed with a streaked spectrograph provides a signal level sufficient for {approximately} 0.06 {angstrom} wavelength shift measurements in a mock-up of an ion diode experiment.

  16. Study on Experiment of Absorption Spectroscopy Detection of Pesticide Residues of Carbendazim in Orange Juice%橙汁中多菌灵农药残留吸收光谱特征研究

    季仁东; 陈梦岚; 赵志敏; 朱星玥; 王乐新; 刘全金

    2014-01-01

    利用分光光度计,通过对多菌灵及橙汁-多菌灵混合体系的紫外-可见吸收光谱进行研究,得到橙汁中不同农药含量下的吸收光谱特征,分析了吸光度与多菌灵农药含量的关系。研究表明:多菌灵药液在285 nm处有较强的特征吸收峰。通过向橙汁中逐量添加0.28 mg · mL -1多菌灵标准溶液,与纯多菌灵药液吸收光谱比较,发现峰值位置出现了小幅度蓝移(285~280 nm ),说明橙汁和多菌灵发生了相互作用,通过对280 nm波长处的吸光度与多菌灵药液含量进行最小二乘法线性拟合,建立了橙汁中吸光度与多菌灵农药含量之间的预测模型,发现吸光度与多菌灵药剂含量具有很好的线性关系,其线性函数模型为:I=2.41+9.26 x ,相关系数为0.996,回收率在81%~102%之间。根据该回归模型,可以得到橙汁中多菌灵农药残留量的准确值,从而验证了利用紫外-可见吸收光谱测定橙汁中多菌灵残留量的方法的可行性。研究表明,利用光谱技术直接对果汁中农药残留检测方法是可行的,能够满足快速分析的需要,本研究为农药残留检测提供了新的途径。%Absorption spectra were studied for the carbendazim ,in the mixed solution of orange juice and carbendazim using spectrophotometer .The most intensive characteristic peak (285 nm) was found in the spectrum of carbendazim standard solu-tion .Compared with the carbendazim drug solution ,the peak position of absorption spectrum has the blue shift (285~280 nm) when carbendazim(0 .28 mg · mL -1 )was added in the orange juice .So that we can conclude that interaction happened between the orange juice and carbendazim .Through the method of least squares fitting ,the prediction models between the absorbance of orange juice and carbendazim content was obtained with a good linear relationship .The linear function model was :I=2 .41 +9 . 26x ,the correlation

  17. [Measurement on gas temperature distribution by tunable diode laser absorption spectroscopy].

    Li, Ning; Yan, Jian-hua; Wang, Fei; Chi, Yong; Cen, Ke-fa

    2008-08-01

    The technique of tunable diode laser absorption spectroscopy (TDLAS) can be used for gas temperature distribution measurement by scanning multiple gas absorption lines with a tunable diode laser. The fundamental of gas temperature distribution measurement by TDLAS is introduced in the present paper, and the discretization strategy of equation for gas absorption is also given here. Using constrained linear least-square fitting method, the gas temperature distribution can be calculated with the help of physical constraints under the condition of uniform gas concentration and pressure. Based on the spectral parameters of four CO absorption lines near 6330 cm(-1) from HITRAN database, the model of two-temperature distribution at 300 and 600 K with each path length of 55 cm was set up. The effects of relative measurement error and different path length constraints of temperature bins on the gas temperature distribution measurement results were simulated by constrained linear least-square fitting. The results show that the temperature distribution calculation error increases as the relative measurement error rises. A measurement error of 5% could lead to a maximum relative error of 11%, and an average relative error of 2.2% for calculation result. And the weak physical constraints of path length for temperature bins could increase the calculation result error during the process of constrained linear least-square fitting. By setting up the model of two-temperature distribution with gas cells at room temperature as the cold section and in tube furnace as the hot section, the experiment of gas temperature distribution measurement in lab was carried out. Using four absorption lines of CO near 6330 cm(-1) scanned by VCSEL diode laser, and fitting the background laser intensity without absorption by the cubic polynomial to get the baseline signal, the integrals of spectral absorbance for gas temperature distribution measurement can be calculated. The relative calculation

  18. Nuclear-Motion Effects in Attosecond Transient Absorption Spectroscopy of Molecules

    Bækhøj, Jens E; Madsen, Lars Bojer

    2015-01-01

    We investigate the characteristic effects of nuclear motion on attosecond transient absorption spectra in molecules by calculating the spectrum for different model systems. Two models of the hydrogen molecular ion are considered: one where the internuclear separation is fixed, and one where the nuclei are free to vibrate. The spectra for the fixed nuclei model are similar to atomic spectra reported elsewhere, while the spectra obtained in the model including nuclear motion are very different and dominated by extremely broad absorption features. These broad absorption features are analyzed and their relation to molecular dissociation investigated. The study of the hydrogen molecular ion validates an approach based on the Born-Oppenheimer approximation and a finite electronic basis. This latter approach is then used to study the three-dimensional hydrogen molecule including nuclear vibration. The spectrum obtained from H$_2$ is compared to the result of a fixed-nuclei calculation. In the attosecond transient ab...

  19. In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas.

    Adato, Ronen; Altug, Hatice

    2013-01-01

    Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules' native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology.

  20. 21-cm absorption studies with the Square Kilometer Array

    Kanekar, N; Briggs, FH

    2004-01-01

    HI 21-cm absorption spectroscopy provides an excellent probe of the neutral gas content of absorbing galaxies, yielding information on their kinematics, mass, physical size and ISM conditions. The high sensitivity, unrivaled frequency coverage and RFI suppression techniques of the SKA will enable it

  1. Autler-Townes triplet absorption spectroscopy, controllable electromagnetically induced transparency and nonlinear coherence Kerr effect

    Bacha, Bakht Amin; Nazmidinov, Rashid G

    2014-01-01

    A Field Generated Coherence (FGC)' based 3-field cyclically-driven 4-level atomic system, which is an extended version of $\\Lambda$ type schemes, is investigated for Autler-Townes triplet absorption (ATT) spectroscopy. Two dark lines which appear in the ATT spectrum, are the essence of the generated multiple controllable EIT windows for a superluminal Gaussian light pulse. We also investigate enhancement in the group velocity for the Gaussian light pulse, using a nonlinear coherence Kerr effect. Consequently, the superluminal probing pulse leaves a steep anomalous region of the medium by $28 \\mu s$ sooner than the light pulse of the Kerr-free system. A co-linear propagation of the driving fields is suggested to minimize our explored Doppler broadening incoherence effect on the probe pulse. Indeed, the analytically observed undistorted retrieved light pulse, which is a necessary and useful requirement for realization of the results in laboratory, is also shown and analyzed explicitly.

  2. Reflection mode X-ray absorption spectroscopy: new applications in surface science research

    Luetzenkirchen-Hecht, Dirk [Institut fuer Experimentalphysik und Institut fuer Materialwissenschaften, Fachbereich C-Physik, Bergische Universitaet Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany)]. E-mail: dirklh@uni-wuppertal.de; Frahm, Ronald [Institut fuer Experimentalphysik und Institut fuer Materialwissenschaften, Fachbereich C-Physik, Bergische Universitaet Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany)

    2005-02-28

    Reflection mode grazing incidence X-ray absorption spectroscopy (GIXAFS) was applied for the in situ investigation of solid/liquid interfaces. Results obtained during the active dissolution of metals are presented. In the case of silver in neutral or weakly acidic Na{sub 2}SO{sub 4} solutions (pH 6.5), the formation of an Ag-O species at the surface of the Ag-electrode can be proven, i.e. the active dissolution proceeds via a non-protecting surface layer, the thickness of which was estimated to be about 5 nm. The atomic short-range order of this surface layer is different from polycrystalline silver oxides (Ag{sub 2}O and AgO) and relates to a more disordered or amorphous Ag{sup 1+} oxide.

  3. Etalon-induced baseline drift and correction in atom flux sensors based on atomic absorption spectroscopy

    Du, Yingge; Chambers, Scott A.

    2014-10-01

    Atom flux sensors based on atomic absorption (AA) spectroscopy are of significant interest in thin film growth as they can provide unobtrusive, element specific real-time flux sensing and control. The ultimate sensitivity and performance of these sensors are strongly affected by baseline drift. Here we demonstrate that an etalon effect resulting from temperature changes in optical viewport housings is a major source of signal instability, which has not been previously considered, and cannot be corrected using existing methods. We show that small temperature variations in the fused silica viewports can introduce intensity modulations of up to 1.5% which in turn significantly deteriorate AA sensor performance. This undesirable effect can be at least partially eliminated by reducing the size of the beam and tilting the incident light beam off the viewport normal.

  4. Etalon-induced Baseline Drift And Correction In Atom Flux Sensors Based On Atomic Absorption Spectroscopy

    Du, Yingge; Chambers, Scott A.

    2014-10-20

    Atom flux sensors based on atomic absorption (AA) spectroscopy are of significant interest in thin film growth as they can provide unobtrusive, element specific, real-time flux sensing and control. The ultimate sensitivity and performance of the sensors are strongly affected by the long-term and short term baseline drift. Here we demonstrate that an etalon effect resulting from temperature changes in optical viewport housings is a major source of signal instability which has not been previously considered or corrected by existing methods. We show that small temperature variations in the fused silica viewports can introduce intensity modulations of up to 1.5%, which in turn significantly deteriorate AA sensor performance. This undesirable effect can be at least partially eliminated by reducing the size of the beam and tilting the incident light beam off the viewport normal.

  5. Etalon-induced baseline drift and correction in atom flux sensors based on atomic absorption spectroscopy

    Du, Yingge, E-mail: yingge.du@pnnl.gov [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Chambers, Scott A. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

    2014-10-20

    Atom flux sensors based on atomic absorption (AA) spectroscopy are of significant interest in thin film growth as they can provide unobtrusive, element specific real-time flux sensing and control. The ultimate sensitivity and performance of these sensors are strongly affected by baseline drift. Here we demonstrate that an etalon effect resulting from temperature changes in optical viewport housings is a major source of signal instability, which has not been previously considered, and cannot be corrected using existing methods. We show that small temperature variations in the fused silica viewports can introduce intensity modulations of up to 1.5% which in turn significantly deteriorate AA sensor performance. This undesirable effect can be at least partially eliminated by reducing the size of the beam and tilting the incident light beam off the viewport normal.

  6. [Determination of trace selenium in edible fungi with graphite furnace atomic absorption spectroscopy].

    Tie, Mei; Zhang, Wei; Li, Jing; Jing, Kui; Zang, Shu-liang; Li, Hua-wei

    2006-01-01

    In the present article, samples were digested by a quartz high-pressure digestion pot, reducing the loss of selenium in digestion. The content of selenium in edible fungi was determined by using graphite furnace atomic absorption spectroscopy, and the results showed that when the content of selenium in edible fungi was determined by using 1% Ni(NO3)2 as a matrix modifier, ashing temperature of 500 degreed C, and atomization temperature of 2 500 degrees C, and rectifying background by deuterium light, the recovery was in the range of 92.1%-115.5%, the relative standard deviation of the method was 1.28%, and the limit of detection was 15.8 microg x L(-1). The method was suitable for the determination of trace selenium in edible fungi with the advantages of being simple, rapid, sensitive, stable and accurate etc., and the results were satisfactory.

  7. Detection of the transient PNO molecule by infrared laser absorption spectroscopy

    Bell, I. S.; Hamilton, P. A.; Davies, P. B.

    The PNO molecule has been observed in the gas phase for the first time. Some 200 vibrationrotation transitions were detected in the 1760cm-1 region using infrared diode laser absorption spectroscopy in a long path cell. Most of the lines can be assigned to the (001)←(000) stretching fundamental and (011)←(010) hot band transitions. The fundamental band exhibits a perturbation at high rotational levels which leads to a unique assignment of the rotational numbering. The effective rotational constants determined are in good agreement with ab initio predictions and the band origin, 1756.64586(24)cm-1, is very close to the matrix value. A tentative rotational assignment of the hot band transitions has been made which gives a band origin of 1748.388cm-1.

  8. High precision measurement of formaldehyde in air with differential optical absorption spectroscopy

    2007-01-01

    The formaldehyde (HCHO) measurement is described by differential optical absorption spectroscopy (DOAS) technique and the data processing method is discussed in detail, including the selection of retrieval wavelength band, the removing of interfering structures, the steps of data processing and the spectrum dealing with nonlinear method. The HCHO concentration retrieved in different wavelength bands were compared, including relative error, repeatability and detection limit. As a result, the band from 314 to 332 nm was most suitable for the retrieval of HCHO. With these methods, high measurement precision of 1.9% was obtained and the detection limit of HCHO is less than 1.5 ppb. In addition, high linear relativity 0.9999 is achieved by measuring five different concentrations of HCHO with this system.

  9. Performance improvements in temperature reconstructions of 2-D tunable diode laser absorption spectroscopy (TDLAS)

    Choi, Doo-Won; Jeon, Min-Gyu; Cho, Gyeong-Rae; Kamimoto, Takahiro; Deguchi, Yoshihiro; Doh, Deog-Hee

    2016-02-01

    Performance improvement was attained in data reconstructions of 2-dimensional tunable diode laser absorption spectroscopy (TDLAS). Multiplicative Algebraic Reconstruction Technique (MART) algorithm was adopted for data reconstruction. The data obtained in an experiment for the measurement of temperature and concentration fields of gas flows were used. The measurement theory is based upon the Beer-Lambert law, and the measurement system consists of a tunable laser, collimators, detectors, and an analyzer. Methane was used as a fuel for combustion with air in the Bunsen-type burner. The data used for the reconstruction are from the optical signals of 8-laser beams passed on a cross-section of the methane flame. The performances of MART algorithm in data reconstruction were validated and compared with those obtained by Algebraic Reconstruction Technique (ART) algorithm.

  10. Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

    Sheps, Leonid; Chandler, David W.

    2013-04-01

    Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

  11. Accurate frequency of the 119 micron methanol laser from tunable far-infrared absorption spectroscopy

    Inguscio, M.; Zink, L. R.; Evenson, K. M.; Jennings, D. A.

    1990-01-01

    High-accuracy absorption spectroscopy of CH3OH in the far infrared is discussed. In addition to 22 transitions in the ground state, the frequency of the (n, tau, J, K), (0, 1, 16, 8) to (0, 2, 15, 7) transition in the nu5 excited vibrational level, which is responsible for the laser emission at 119 microns, was measured. The measured frequency is 2,522,782.57(10) MHz at zero pressure, with a pressure shift of 6.1(32) kHz/Pa (0.805/420/ MHz/torr). An accurate remeasurement of the laser emission frequency has also been performed, and the results are in good agreement.

  12. Site- and phase-selective x-ray absorption spectroscopy based on phase-retrieval calculation

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Matsubara, Eiichiro

    2017-03-01

    Understanding the chemical state of a particular element with multiple crystallographic sites and/or phases is essential to unlocking the origin of material properties. To this end, resonant x-ray diffraction spectroscopy (RXDS) achieved through a combination of x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques can allow for the measurement of diffraction anomalous fine structure (DAFS). This is expected to provide a peerless tool for electronic/local structural analyses of materials with complicated structures thanks to its capability to extract spectroscopic information about a given element at each crystallographic site and/or phase. At present, one of the major challenges for the practical application of RXDS is the rigorous determination of resonant terms from observed DAFS, as this requires somehow determining the phase change in the elastic scattering around the absorption edge from the scattering intensity. This is widely known in the field of XRD as the phase problem. The present review describes the basics of this problem, including the relevant background and theory for DAFS and a guide to a newly-developed phase-retrieval method based on the logarithmic dispersion relation that makes it possible to analyze DAFS without suffering from the intrinsic ambiguities of conventional iterative-fitting. Several matters relating to data collection and correction of RXDS are also covered, with a final emphasis on the great potential of powder-sample-based RXDS (P-RXDS) to be used in various applications relevant to practical materials, including antisite-defect-type electrode materials for lithium-ion batteries.

  13. Broadband absorption spectroscopy by combining frequency-domain and steady-state techniques

    Berger, Andrew J.; Bevilacqua, Frederic; Jakubowski, Dorota B.; Cerussi, Albert E.; Butler, John A.; Hsiang, D.; Tromberg, Bruce J.

    2001-06-01

    A technique for measuring broadband near-infrared absorption spectra of turbid media is presented using a combination of frequency-domain (FD) and steady-state (SS) reflectance methods. Most of the wavelength coverage is provided by a white-light SS measurement, while the FD data are acquired at a few selected wavelengths. Coefficients of absorption ((mu) a) and reduced scattering ((mu) s') derived from the FD data are used to intensity-calibrate the SS measurements and to estimate (mu) s' at all wavelengths in the spectral window of interest. After these steps are performed, (mu) a can be determined by comparing the SS reflectance values to the predictions of diffusion theory, wavelength by wavelength. We present an application of this method to breast tumor characterization. A case study of a fibroadenoma is shown, where different absorption spectra were found between the normal and the tumor sides.

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

    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

  15. Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

    Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

    2017-02-01

    X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

  16. Grazing incidence reflectivity and total electron yield effects in soft x-ray absorption spectroscopy

    Alders, D; Hibma, T; Sawatzky, G.A; Cheung, K.C.; van Dorssen, G.E.; Roper, M.D.; Padmore, H.A.; van der Laan, G.; Vogel, J; Sacchi, M.

    1997-01-01

    We report on a study of grazing incidence absorption and reflection spectra of NiO in the region of the Ni 2p edge. The aim is to evaluate the distortion of the near edge spectrum by the critical angle behavior of individual components within the spectrum. This can be used to improve the separation

  17. Use of flameless atomic absorption spectroscopy in immune cytolysis for nonradioactive determination of killer cell activity.

    Borella, P; Bargellini, A; Salvioli, S; Cossarizza, A

    1996-02-01

    We describe here a novel method to evaluate natural killer (NK) cytolytic activity by use of flameless atomic absorption spectroscopy (GF-AAS). This technique may be adopted for use in laboratories equipped with electrothermal atomic absorption spectrometers. Nonradioactive Cr as Na2CrO4 was used to label target cells (K562), and cell lysis was evaluated by measuring Cr released after 4 h of incubation with the effectors. We selected 520 micrograms/L as the optimal dose for labeling targets, between 12 and 20 h as the optimal incubation time, and 10(4) cells as the optimal target size. Advantages of this method include: (a) exclusion of radioactive tracer, with no risk for workers; (b) limited costs; (c) high sensitivity and reproducibility; (d) possibility to store samples; and (e) better control of Cr used for labeling cells due to well-determined, fixed Cr concentrations in the range of nontoxic and linear cellular uptake. Comparison with data obtained by conventional 51Cr labeling of targets killed by the same effectors was excellent, yielding comparable results and corroborating the method.

  18. Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules

    Bui, Tung S.; Dao, Thang D.; Dang, Luu H.; Vu, Lam D.; Ohi, Akihiko; Nabatame, Toshihide; Lee, YoungPak; Nagao, Tadaaki; Hoang, Chung V.

    2016-01-01

    From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3′-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes. PMID:27555217

  19. Measurement of Gas Temperature in Negative Hydrogen Ion Source by Wavelength-Modulated Laser Absorption Spectroscopy

    Nishiyama, S.; Sasaki, K.; Nakano, H.; Goto, M.; Kisaki, M.; Tsumori, K.; NIFS-NBI Team

    2014-10-01

    Measurement of the energy distribution of hydrogen atom is important and essential to understand the production mechanism of its negative ion (H-) in cesium-seeded negative ion sources. In this work, we evaluated the temperature of atomic hydrogen in the large-scale arc-discharge negative hydrogen ion source in NIFS by wavelength-modulated laser absorption spectroscopy. The laser beam was passed through the adjacent region to the grid electrode for extracting negative ions. The frequency of the laser was scanned slowly over the whole range of the Doppler width (100 GHz in 1s). A sinusoidal frequency modulation at 600 Hz with a width of 30 GHz was superposed onto the slow modulation. The transmitted laser was detected using a photodiode, and its second harmonic component of the sinusoidal modulation was amplified using a lock-in amplifier. The obtained spectrum was in good agreement with an expected spectrum of the Doppler-broadened Balmer- α line. The estimated temperature of atomic hydrogen was approximately 3000 K. The absorption increased with the arc-discharge power, while the temperature was roughly independent of the power. This work is supported by the NIFS Collaboration Research Program NIFS13KLER021.

  20. Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules

    Bui, Tung S.; Dao, Thang D.; Dang, Luu H.; Vu, Lam D.; Ohi, Akihiko; Nabatame, Toshihide; Lee, Youngpak; Nagao, Tadaaki; Hoang, Chung V.

    2016-08-01

    From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3‧-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes.

  1. Time-resolved tunable diode laser absorption spectroscopy of pulsed plasma.

    Adámek, P; Olejníček, J; Čada, M; Kment, Š; Hubička, Z

    2013-07-15

    A method for time-resolved tunable diode laser absorption spectroscopy (LAS) has been developed. In this Letter, we describe in detail a developed electronic module that controls the time resolution of the LAS system. The transistor-transistor logic signal triggering the plasma pulse is used for generation of two signals: the first one triggers fine tuning of the laser wavelength and the second one controls time-defined signal sampling from the absorption detector. The described method and electronic system enable investigation of the temporal evolution of the density and temperature of selected particles in technological plasma systems. The high-power impulse magnetron sputtering system with a period of 10 ms and a duty cycle of 1% has been used to verify this method. The temporal evolution of argon metastable density was measured in the active part of the pulse and in the afterglow. The resulting density of Ar* displays a double-peak structure with a first peak in the plasma "ON" phase and a second peak in the afterglow approximately 1 ms after the end of the pulse.

  2. Protein dynamics in an intermediate state of myoglobin: optical absorption, resonance Raman spectroscopy, and x-ray structure analysis.

    N. Engler; Ostermann, A; Gassmann, A.; Lamb, D C; Prusakov, V E; J. Schott; Schweitzer-Stenner, R; Parak, F. G.

    2000-01-01

    A metastable state of myoglobin is produced by reduction of metmyoglobin at low temperatures. This is done either by irradiation with x-rays at 80 K or by electron transfer from photoexcited tris(2, 2'-bipyridine)-ruthenium(II) at 20 K. At temperatures above 150 K, the conformational transition toward the equilibrium deoxymyoglobin is observed. X-ray crystallography, Raman spectroscopy, and temperature-dependent optical absorption spectroscopy show that the metastable state has a six-ligated ...

  3. Multipitched Diffraction Gratings for Surface Plasmon Resonance-Enhanced Infrared Reflection Absorption Spectroscopy.

    Petefish, Joseph W; Hillier, Andrew C

    2015-11-03

    We demonstrate the application of metal-coated diffraction gratings possessing multiple simultaneous pitch values for surface enhanced infrared absorption (SEIRA) spectroscopy. SEIRA increases the magnitude of vibrational signals in infrared measurements by one of several mechanisms, most frequently involving the enhanced electric field associated with surface plasmon resonance (SPR). While the majority of SEIRA applications to date have employed nanoparticle-based plasmonic systems, recent advances have shown how various metals and structures lead to similar signal enhancement. Recently, diffraction grating couplers have been demonstrated as a highly tunable platform for SEIRA. Indeed, gratings are an experimentally advantageous platform due to the inherently tunable nature of surface plasmon excitation at these surfaces since both the grating pitch and incident angle can be used to modify the spectral location of the plasmon resonance. In this work, we use laser interference lithography (LIL) to fabricate gratings possessing multiple pitch values by subjecting photoresist-coated glass slides to repetitive exposures at varying orientations. After metal coating, these gratings produced multiple, simultaneous plasmon peaks associated with the multipitched surface, as identified by infrared reflectance measurements. These plasmon peaks could then be coupled to vibrational modes in thin films to provide localized enhancement of infrared signals. We demonstrate the flexibility and tunability of this platform for signal enhancement. It is anticipated that, with further refinement, this approach might be used as a general platform for broadband enhancement of infrared spectroscopy.

  4. Towards a standard for the dynamic measurement of pressure based on laser absorption spectroscopy

    Douglass, K. O.; Olson, D. A.

    2016-06-01

    We describe an approach for creating a standard for the dynamic measurement of pressure based on the measurement of fundamental quantum properties of molecular systems. From the linewidth and intensities of ro-vibrational transitions we plan on making an accurate determination of pressure and temperature. The goal is to achieve an absolute uncertainty for time-varying pressure of 5% with a measurement rate of 100 kHz, which will in the future serve as a method for the traceable calibration of pressure sensors used in transient processes. To illustrate this concept we have used wavelength modulation spectroscopy (WMS), due to inherent advantages over direct absorption spectroscopy, to perform rapid measurements of carbon dioxide in order to determine the pressure. The system records the full lineshape profile of a single ro-vibrational transition of CO2 at a repetition rate of 4 kHz and with a systematic measurement uncertainty of 12% for the linewidth measurement. A series of pressures were measured at a rate of 400 Hz (10 averages) and from these measurements the linewidth was determined with a relative uncertainty of about 0.5% on average. The pressures measured using WMS have an average difference of 0.6% from the absolute pressure measured with a capacitance diaphragm sensor.

  5. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

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

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  6. A cylindrical furnace for absorption spectral studies

    R Venkatasubramanian

    2001-06-01

    A cylindrical furnace with three heating zones, capable of providing a temperature of 1100°C, has been fabricated to enable recording of absorption spectra of high temperature species. The temperature of the furnace can be controlled to ± 1°C of the set temperature. The salient feature of this furnace is that the material being heated can be prevented from depositing on the windows of the absorption cell by maintaining a higher temperature at both the ends of the absorption cell.

  7. High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

    Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

    1995-01-01

    The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

  8. Time-resolved detection of temperature, concentration, and pressure in a shock tube by intracavity absorption spectroscopy

    Fjodorow, Peter; Fikri, Mustapha; Schulz, Christof; Hellmig, Ortwin; Baev, Valery M.

    2016-06-01

    In this paper, we demonstrate the first application of intracavity absorption spectroscopy (ICAS) for monitoring species concentration, total pressure, and temperature in shock-tube experiments. ICAS with a broadband Er3+-doped fiber laser is applied to time-resolved measurements of absorption spectra of shock-heated C2H2. The measurements are performed in a spectral range between 6512 and 6542 cm-1, including many absorption lines of C2H2, with a time resolution of 100 µs and an effective absorption path length of 15 m. Up to 18-times increase of the total pressure and a temperature rise of up to 1200 K have been monitored. Due to the ability of simultaneously recording many absorption lines in a broad spectral range, the presented technique can also be applied to multi-component analysis of transient single-shot processes in reactive gas mixtures in shock tubes, pulse detonation engines, or explosions.

  9. Cyclic voltammetry and near edge X-ray absorption fine structure spectroscopy at the Ag L3-edge on electrochemical halogenation of Ag layers on Au(111)

    Endo, Osamu; Nakamura, Masashi

    2011-05-01

    One to three layers of Ag grown on a Au(111) electrode were studied by cyclic voltammetry in chloride and bromide solutions and by ex-situ near-edge X-ray absorption fine structure spectroscopy at the Ag L3-edge (Ag L3-NEXAFS). The one and two layers obtained by underpotential deposition exhibited reduced intensity at the absorption edge in the Ag L3-NEXAFS spectra, which suggests the gain of d-electrons in these layers. The cyclic voltammograms and the Ag L3-NEXAFS spectra indicate that the second and third layers of Ag halogenated at positive potentials, whereas the first layer remained in metallic form.

  10. Evaluation of trace elements in chewing tobacco and snuff using instrumental neutron activation analysis (INAA) and atomic absorption spectroscopy (AAS)

    Waheed, S.; Siddique, N.; Rahman, S. [Chemistry Div., Directorate of Science, Pakistan Inst. of Nuclear Science and Tech., Islamabad (Pakistan)

    2009-07-01

    Nine samples of chewing tobacco, snuff, tobacco leaf and ash were analyzed using Instrumental Neutron Activation Analysis (INAA) and Atomic Absorption Spectroscopy (AAS). Almost all samples of chewing tobacco and snuff studied in this work contain substantial amounts of Mg, Mn, Na, K. V. Sc, Rb and Fe. Furthermore, varying amounts of Al, Ba, Ca, Ce, Co and Zn were also detected in all tobacco samples. Of the toxic elements which were determined using INAA. As, Sb and Hg were quantified in only few tobacco samples. However, other toxic elements, which were determined using AAS, such as Cu, Pb and Cd were detected in almost all samples of chewing tobacco and snuff. The concentration of majority of the detected elements is high in ash samples which imply that most elements in chewing tobacco and snuff may originate from the addition of ash. (orig.)

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

    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.

  12. Fe-heme structure in Cu, Zn superoxide dismutase from Haemophilus ducreyi by X-ray absorption spectroscopy.

    D'Angelo, Paola; Zitolo, Andrea; Pacello, Francesca; Mancini, Giordano; Proux, Olivier; Hazemann, Jean Louis; Desideri, Alessandro; Battistoni, Andrea

    2010-06-01

    We have carried out an X-ray Absorption Spectroscopy (XAS) study of ferric, ferrous, CO- and NO-bound Haemophilus ducreyi Cu,ZnSOD (HdSOD) in solution to investigate the structural modifications induced by the binding of small gaseous ligands to heme in this enzyme. The combined analysis of EXAFS and XANES data has allowed us to characterize the local structure around the Fe-heme with 0.02A accuracy, revealing a heterogeneity in the distances between iron and the two histidine ligands which was not evident in the X-ray crystal structure. In addition, we have shown that the metal oxidation state does not influence the Fe-heme coordination environment, whereas the presence of the CO and NO ligands induces local structural rearrangements in the enzyme which are very similar to those already observed in other hexa-coordinated heme proteins, such as neuroglobin.

  13. Reactions of cytotoxic metallodrugs with lysozyme in pure DMSO explored through UV-Vis absorption spectroscopy and ESI MS.

    Marzo, Tiziano; Savić, Aleksandar; Massai, Lara; Michelucci, Elena; Sabo, Tibor J; Grguric-Šipka, Sanja; Messori, Luigi

    2015-04-01

    The reactions of four representative metallodrugs with the model protein HEWL were investigated within a non-aqueous environment-i.e. in pure DMSO- through UV-Vis absorption spectroscopy and ESI MS analysis. Notably, formation of a variety of metallodrug-protein adducts was clearly documented. This is the first example for this kind of protein metalation reactions carried out within a pure organic solvent. It is shown that the applied solution conditions greatly affect the nature of the formed adducts, this being well accounted for by the fact that the overall protein conformation is greatly perturbed within pure DMSO; in addition, the activation profiles of the studied metallodrugs are also highly dependent on the nature of the solvent. The implications of these results are discussed.

  14. [Study on transient absorption spectrum of tungsten nanoparticle with HepG2 tumor cell].

    Cao, Lin; Shu, Xiao-Ning; Liang, Dong; Wang, Cong

    2014-07-01

    Significance of this study lies in tungsten nano materials can be used as a preliminary innovative medicines applied basic research. This paper investigated the inhibition of tungsten nanoparticles which effected on human hepatoma HepG2 cells by MTT. The authors use transient absorption spectroscopy (TAS) technology absorption and emission spectra characterization of charge transfer between nanoparticles and tumor cell. The authors discussed the role of the tungsten nanoparticles in the tumor early detection of the disease and its anti-tumor properties. In the HepG2 experiments system, 100-150 microg x mL(-1) is the best drug concentration of anti-tumor activity which recact violently within 6 hours and basically completed in 24 hours. The results showed that transient absorption spectroscopy can be used as tumor detection methods and characterization of charge transfer between nano-biosensors and tumor cells. Tungsten nanoparticles have potential applications as anticancer drugs.

  15. Two instruments based on differential optical absorption spectroscopy (DOAS) to measure accurate ammonia concentrations in the atmosphere

    Volten, H.; Bergwerff, J.B.; Haaima, M.; Lolkema, D.E.; Berkhout, A.J.C.; Hoff, G.R.; Potma, C.J.M.; Wichink Kruit, R.J.; Pul, van W.A.J.; Swart, D.P.J.

    2012-01-01

    We present two Differential Optical Absorption Spectroscopy (DOAS) instruments built at RIVM: the RIVM DOAS and the miniDOAS. Both instruments provide virtually interference-free measurements of NH3 concentrations in the atmosphere, since they measure over an open path, without suffering from inlet

  16. A Simplified Digestion Protocol for the Analysis of Hg in Fish by Cold Vapor Atomic Absorption Spectroscopy

    Kristian, Kathleen E.; Friedbauer, Scott; Kabashi, Donika; Ferencz, Kristen M.; Barajas, Jennifer C.; O'Brien, Kelly

    2015-01-01

    Analysis of mercury in fish is an interesting problem with the potential to motivate students in chemistry laboratory courses. The recommended method for mercury analysis in fish is cold vapor atomic absorption spectroscopy (CVAAS), which requires homogeneous analyte solutions, typically prepared by acid digestion. Previously published digestion…

  17. Investigation Of Li{sub X}CoO{sub 2} Li- Intercalation Electrodes Using X-Ray Absorption Spectroscopy

    Haas, O.; Holzapfel, M.; Yang, X.Q. [BNL Lab (United States); Yoon, W.-S. [BNL Lab (United States); Chung, K.-Y. [BNL Lab (United States)

    2005-03-01

    Li{sub X}CoO{sub 2} was investigated with X-ray absorption spectroscopy using hard and soft X-rays and compared with some results obtained in previous investigations of La{sub (1-x)}-Ca{sub x}CoO{sub 3}, which has a similar electron configuration. (author)

  18. Beyond structure: ultrafast X-ray absorption spectroscopy as a probe of non-adiabatic wavepacket dynamics.

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

    2016-12-16

    The excited state non-adiabatic dynamics of polyatomic molecules, leading to the coupling of structural and electronic dynamics, is a fundamentally important yet challenging problem for both experiment and theory. Ongoing developments in ultrafast extreme vacuum ultraviolet (XUV) and soft X-ray sources present new probes of coupled electronic-structural dynamics because of their novel and desirable characteristics. As one example, inner-shell spectroscopy offers localized, atom-specific probes of evolving electronic structure and bonding (via chemical shifts). In this work, we present the first on-the-fly ultrafast X-ray time-resolved absorption spectrum simulations of excited state wavepacket dynamics: photo-excited ethylene. This was achieved by coupling the ab initio multiple spawning (AIMS) method, employing on-the-fly dynamics simulations, with high-level algebraic diagrammatic construction (ADC) X-ray absorption cross-section calculations. Using the excited state dynamics of ethylene as a test case, we assessed the ability of X-ray absorption spectroscopy to project out the electronic character of complex wavepacket dynamics, and evaluated the sensitivity of the calculated spectra to large amplitude nuclear motion. In particular, we demonstrate the pronounced sensitivity of the pre-edge region of the X-ray absorption spectrum to the electronic and structural evolution of the excited-state wavepacket. We conclude that ultrafast time-resolved X-ray absorption spectroscopy may become a powerful tool in the interrogation of excited state non-adiabatic molecular dynamics.

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

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

    2015-12-14

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

  20. Metastable argon atom density in complex argon/acetylene plasmas determined by means of optical absorption and emission spectroscopy

    Sushkov, Vladimir; Herrendorf, Ann-Pierra; Hippler, Rainer

    2016-10-01

    Optical emission and absorption spectroscopy has been utilized to investigate the instability of acetylene-containing dusty plasmas induced by growing nano-particles. The density of Ar(1s5) metastable atoms was derived by two methods: tunable diode laser absorption spectroscopy and with the help of the branching ratio method of emitted spectral lines. Results of the two techniques agree well with each other. The density of Ar(1s3) metastable atoms was also measured by means of optical emission spectroscopy. The observed growth instability leads to pronounced temporal variations of the metastable and other excited state densities. An analysis of optical line ratios provides evidence for a depletion of free electrons during the growth cycle but no indication for electron temperature variations.

  1. X-ray absorption spectroscopy characterization of Zn underpotential deposition on Au(1 1 1) from phosphate supporting electrolyte

    Lee, Jonathan R.I., E-mail: lee204@llnl.go [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); O' Malley, Rachel L.; O' Connell, Timothy J. [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Vollmer, Antje [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Helmholtz Zentrum Berlin f. Materialien und Energie, BESSY II, Albert-Einstein-Str. 15, 12489 Berlin (Germany); Rayment, Trevor, E-mail: trevor.rayment@diamond.ac.u [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom)

    2010-12-01

    Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(1 1 1) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate ({radical}3 x {radical}3)R30{sup o} ({theta}{sub sc} = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(1 1 1) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a ({radical}3 x {radical}3)R30{sup o} ({theta}{sub sc} = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(1 1 1). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(1 1 1) system.

  2. X-ray Absorption Spectroscopy Characterization of Zn Underpotential Deposition on Au(111) from Phosphate Supporting Electrolyte

    Lee, J R; O' Malley, R L; O' Connell, T J; Vollmer, A; Rayment, T

    2009-12-11

    Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(111) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(111) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(111). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(111) system.

  3. Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

    Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

    2016-01-01

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge. PMID:26908198

  4. Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy.

    Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

    2016-02-24

    Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

  5. Two-Dimensional UV Absorption Correlation Spectroscopy as a Method for the Detection of Thiamethoxam Residue in Tea

    Zhang, J.; Zhao, Zh.; Wang, L.; Zhu, X.; Shen, L.; Yu, Y.

    2015-05-01

    Two-dimensional correlation spectroscopy (2D-COS) combined with UV absorption spectroscopy was evaluated as a technique for the identification of spectral regions associated with the residues of thiamethoxam in tea. There is only one absorption peak at 275 nm in the absorption spectrum of a mixture of thiamethoxam and tea, which is the absorption peak of tea. Based on 2D-COS, the absorption peak of thiamethoxam at 250 nm is extracted from the UV spectra of the mixture. To determine the residue of thiamethoxam in tea, 250 nm is selected as the measured wavelength, at which the fitting result is as follows: the residual sum of squares is 0.01375, standard deviation R2 is 0.99068, and F value is 426. Statistical analysis shows that there is a significant linear relationship between the concentration of thiamethoxam in tea and the absorbance at 250 nm in the UV spectra of the mixture. Moreover, the average prediction error is 0.0033 and the prediction variance is 0.1654, indicating good predictive result. Thus, the UV absorption spectrum can be used as a measurement method for rapid detection of thiamethoxam residues in tea.

  6. Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy

    W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

    2011-12-31

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal-binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  7. X-ray absorption spectroscopy in biological systems. Opportunities and limitations

    Bovenkamp, Gudrun Lisa

    2013-05-15

    X-ray absorption spectroscopy has become more important for applications in the material sciences, geology, environmental science and biology, specifically in the field of molecular biology. The scope of this thesis is to add more experimental evidence in order to show how applicable X-ray absorption near edge structure (XANES) is to biology. Two biological systems were investigated, at the molecular level, lead uptake in plants and the effect of silver on bacteria. This investigation also included an analysis of the sensitivity of Pb L{sub 3}- and Ag L{sub 3}-XANES spectra with regard to their chemical environment. It was shown that Pb L{sub 3}- and Ag L{sub 3}-XANES spectra are sensitive to an environment with at least differences in the second coordination shell. The non-destructive and element specific properties of XANES are the key advantages that were very important for this investigation. However, in both projects the adequate selection of reference compounds, which required in some cases a chemical synthesis, was the critical factor to determine the chemical speciation and, finally, possible uptake and storage mechanisms for plants and antibacterial mechanisms of silver. The chemical environment of Pb in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel mountains in Germany was determined using both solid compounds and aqueous solutions of different ionic strength, which simulate the plant environment. The results can be interpreted in such a way that lead is sorbed on the surface of cell walls. Silver bonding as reaction with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli bacteria was determined using inorganic silver compounds and synthesized silver amino acids. Silver binds to sulfur, amine and carboxyl groups in amino acids.

  8. In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

    McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.; Majidi, Hasti; Bunker, Bruce A.; Baxter, Jason B. (Drexel); (Notre)

    2010-12-03

    Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example, this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.

  9. Sulfur K-edge absorption spectroscopy on selected biological systems; Schwefel-K-Kanten-Absorptionsspektroskopie an ausgewaehlten biologischen Systemen

    Lichtenberg, Henning

    2008-07-15

    Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H{sub 2}S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

  10. Absorption spectroscopy of single red blood cells in the presence of mechanical deformations induced by optical traps

    Wojdyla, Michal; Raj, Saurabh; Petrov, Dmitri

    2012-09-01

    The electronic properties of single human red blood cells under mechanical deformations were investigated using a combination of dual beam optical tweezers and UV-vis absorption spectroscopy. The mechanical deformations were induced by two near-infrared optical traps with different trapping powers and trap configurations. The deformations were applied in two ways: locally, due to the mechanical forces around the traps, and by stretching the cell by moving the traps in opposite directions. In the presence of local deformations, the single cell undergoes a transition from an oxygenated state to a partially deoxygenated state. This process was found to be reversible and strongly power-dependent. Stretching the cell caused an opposite effect, indicating that the electronic response of the whole cell is dominated by the local interaction with the trapping beams. Results are discussed considering light-induced local heating, the Stark effect, and biochemical alterations due to mechanical forces, and are compared with reports of previous Raman spectroscopy studies. The information gained by the analysis of a single red blood cell's electronic response facilitates the understanding of fundamental physiological processes and sheds further light on the cell's mechanochemistry. This information may offer new opportunities for the diagnosis and treatment of blood diseases.

  11. On the evaluation of air mass factors for atmospheric near-ultraviolet and visible absorption spectroscopy

    Perliski, Lori M.; Solomon, Susan

    1993-01-01

    The interpretation of UV-visible twilight absorption measurements of atmospheric chemical constituents is dependent on how well the optical path, or air mass factor, of light collected by the spectrometer is understood. A simple single scattering model and a Monte Carlo radiative transfer scheme have been developed to study the effects of multiple scattering, aerosol scattering, surface albedo and refraction on air mass factors for scattered light observations. At fairly short visible wavelengths (less than about 450 nm), stratospheric air mass factors are found to be relatively insensitive to multiple scattering, surface albedo and refraction, as well as aerosol scattering by background aerosols. Longer wavelengths display greater sensitivity to refraction and aerosol scattering. Tropospheric air mass factors are found to be highly dependent on aerosol scattering, surface albedo and, at long visible wavelengths (about 650 nm), refraction. Absorption measurements of NO2 and O4 are shown to support these conclusions.

  12. Quantification and parametrization of non-linearity effects by higher-order sensitivity terms in scattered light differential optical absorption spectroscopy

    Puķīte, Jānis; Wagner, Thomas

    2016-05-01

    We address the application of differential optical absorption spectroscopy (DOAS) of scattered light observations in the presence of strong absorbers (in particular ozone), for which the absorption optical depth is a non-linear function of the trace gas concentration. This is the case because Beer-Lambert law generally does not hold for scattered light measurements due to many light paths contributing to the measurement. While in many cases linear approximation can be made, for scenarios with strong absorptions non-linear effects cannot always be neglected. This is especially the case for observation geometries, for which the light contributing to the measurement is crossing the atmosphere under spatially well-separated paths differing strongly in length and location, like in limb geometry. In these cases, often full retrieval algorithms are applied to address the non-linearities, requiring iterative forward modelling of absorption spectra involving time-consuming wavelength-by-wavelength radiative transfer modelling. In this study, we propose to describe the non-linear effects by additional sensitivity parameters that can be used e.g. to build up a lookup table. Together with widely used box air mass factors (effective light paths) describing the linear response to the increase in the trace gas amount, the higher-order sensitivity parameters eliminate the need for repeating the radiative transfer modelling when modifying the absorption scenario even in the presence of a strong absorption background. While the higher-order absorption structures can be described as separate fit parameters in the spectral analysis (so-called DOAS fit), in practice their quantitative evaluation requires good measurement quality (typically better than that available from current measurements). Therefore, we introduce an iterative retrieval algorithm correcting for the higher-order absorption structures not yet considered in the DOAS fit as well as the absorption dependence on

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

    Rykaczewski, Krzysztof

    2015-10-01

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

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

    Porta A.

    2016-01-01

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

  15. Measurement of CO2 concentration at high-temperature based on tunable diode laser absorption spectroscopy

    Chen, Jiuying; Li, Chuanrong; Zhou, Mei; Liu, Jianguo; Kan, Ruifeng; Xu, Zhenyu

    2017-01-01

    A diode laser sensor based on absorption spectroscopy has been developed for sensitive measurement of CO2 concentration at high-temperature. Measurement of CO2 can provide information about the extent of combustion and mix in a combustor that may be used to improve fuel efficiency. Most methods of in-situ combustion measurement of CO2 use the spectroscopic parameters taken from database like HITEMP which is mainly derived from the theoretical calculation and remains a high degree of uncertainty in the spectroscopic parameters. A fiber-coupled diode laser system for measurement of CO2 in combustion environment by use of the high-temperature spectroscopic parameters which are obtained by experiment was proposed. Survey spectra of the R(50) line of CO2 at 5007.787 cm-1 were recorded at high-temperature and various pressures to determine line intensities. The line intensities form the theoretical foundation for future applications of this diode laser sensor system. Survey spectra of four test gas mixtures containing 5.01%CO2, 10.01%CO2, 20.08%CO2, and 49.82%CO2 were measured to verify the accuracy of the diode laser sensor system. The measured results indicate that this sensor can measure CO2 concentration with 2% uncertainty in high temperatures.

  16. Detection of Glucose with Atomic Absorption Spectroscopy by Using Oligonucleotide Functionalized Gold Nanoparticle.

    Zhang, Hong; Yan, Honglian; Ling, Liansheng

    2016-06-01

    A novel method for the detection of glucose was established with atomic absorption spectroscopy by using the label of gold nanoparticle (AuNP). Silver-coated glass assembled with oligonucleotide 5'-SH-T12-AGA CAA GAG AGG-3' (Oligo 1) was acted as separation probe, oligonucleotide 5'-CAA CAG AGA ACG-T12-SH-3' modified gold nanoparticle (AuNP-Oligo 2) was acted as signal-reporting probe. Oligonucleotide 5'-CGT TCT CTG TTG CCT CTC TTG TCT-3' (Oligo 3) could hybridize with Oligo 1 on the surface of silver-coated glass and AuNP-Oligo 2, and free AuNP-Oligo 2 could be removed by rinsing with buffer. Hence the concentration of Oligo 3 was transformed into the concentration of gold element. In addition, Oligo 3 could be cleaved into DNA fragments by glucose, glucose oxidase and Fe(2+)-EDTA through Fenton reaction. Thereby the concentration of glucose could be transformed to the absorbance of gold element. Under the optimum conditions, the integrated absorbance decreased proportionally to the concentration of glucose over the range from 50.0 μM to 1.0 mM with a detection limit of 40.0 μM. Moreover, satisfactory result was obtained when the assay was used to determinate glucose in human serum.

  17. Determination of firing distance. Lead analysis on the target by atomic absorption spectroscopy (AAS).

    Gagliano-Candela, Roberto; Colucci, Anna P; Napoli, Salvatore

    2008-03-01

    This paper reports a method for the determination of the firing distance. Atomic absorption spectroscopy (AAS) was used to determine the lead (Pb) pattern around bullet holes produced by shots on test targets from the gun. Test shots were made with a Colt 38 Special at 5, 10, 20, 25, 30, 35, 40, 45, 50, 60, 80, and 100 cm target distance. The target was created with sheets of Whatman no. 1 paper on a polystyrene support. The target was subdivided into three carefully cut out rings (1, 2, and 3; with external diameters of 1.4 cm; 5 cm; 10.2 cm, respectively). Each sample was analyzed with graphite furnace AAS. Lead values analysis performed for each ring yielded a linear relation between the firing distance (cm) and the logarithm of lead amounts (microg/cm(2)) in definite target areas (areas 2 + 3): [ln dPb(2+3) = a(0) + a(1)l]; where dPb(2+3) = lead microg/cm(2) of area 2 + 3; a(0) and a(1) are experimentally calculated; l = distance in cm.

  18. Some problems connected with boron determination by atomic absorption spectroscopy and the sensitivity improvement

    JELENA J. SAVOVIC

    2001-08-01

    Full Text Available Two atomizers were compared: an N2O–C2H2 flame and a stabilized U-shaped DC arc with aerosol supply. Both the high plasma temperature and the reducing atmosphere obtained by acetylene addition to the argon stream substantially increase the sensitivity of boron determination by atomic absorption spectroscopy (AAS when the arc atomizer is used. The results were compared with those for silicon as a control element. The experimental characteristic concentrations for both elements were compared with the computed values. The experimentally obtained characteristic concentration for boron when using the arc atomizer was in better agreement with the calculated value. It was estimated that the influence of stable monoxide formation on the sensitivity for both elements was about the same, but reduction of analyte and formation of non-volatile carbide particles was more important for boron, which is the main reason for the low sensitivity of boron determination using a flame atomizer. The use of an arc atomizer suppresses this interference and significantly improves the sensitivity of the determination.

  19. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

    Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J.

    2016-05-01

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  20. Assessment of the performance of a compact concentric spectrometer system for Atmospheric Differential Optical Absorption Spectroscopy

    C. Whyte

    2009-12-01

    Full Text Available A breadboard demonstrator of a novel UV/VIS grating spectrometer has been developed based upon a concentric arrangement of a spherical meniscus lens, concave spherical mirror and curved diffraction grating suitable for a range of atmospheric remote sensing applications from the ground or space. The spectrometer is compact and provides high optical efficiency and performance benefits over traditional instruments. The concentric design is capable of handling high relative apertures, owing to spherical aberration and comma being near zero at all surfaces. The design also provides correction for transverse chromatic aberration and distortion, in addition to correcting for the distortion called "smile", the curvature of the slit image formed at each wavelength. These properties render this design capable of superior spectral and spatial performance with size and weight budgets significantly lower than standard configurations. This form of spectrometer design offers the potential for exceptionally compact instrument for differential optical absorption spectroscopy (DOAS applications from LEO, GEO, HAP or ground-based platforms. The breadboard demonstrator has been shown to offer high throughput and a stable Gaussian line shape with a spectral range from 300 to 450 nm at 0.5 nm resolution, suitable for a number of typical DOAS applications.

  1. Assessment of the performance of a compact concentric spectrometer system for Atmospheric Differential Optical Absorption Spectroscopy

    C. Whyte

    2009-08-01

    Full Text Available A breadboard demonstrator of a novel UV/VIS grating spectrometer for atmospheric research has been developed based upon a concentric arrangement of a spherical meniscus lens, concave spherical mirror and curved diffraction grating suitable for a range of remote sensing applications from the ground or space. The spectrometer is compact and provides high optical efficiency and performance benefits over traditional instruments. The concentric design is capable of handling high relative apertures, owing to spherical aberration and coma being near zero at all surfaces. The design also provides correction for transverse chromatic aberration and distortion, in addition to correcting for the distortion called "smile", the curvature of the slit image formed at each wavelength. These properties render this design capable of superior spectral and spatial performance with size and weight budgets significantly lower than standard configurations. This form of spectrometer design offers the potential for an exceptionally compact instrument for differential optical absorption spectroscopy (DOAS applications particularly from space (LEO, GEO orbits and from HAPs or ground-based platforms. The breadboard demonstrator has been shown to offer high throughput and a stable Gaussian line shape with a spectral range from 300 to 450 nm at better than 0.5 nm resolution, suitable for a number of typical DOAS applications.

  2. Characterization of metalloproteins by high-throughput X-ray absorption spectroscopy.

    Shi, Wuxian; Punta, Marco; Bohon, Jen; Sauder, J Michael; D'Mello, Rhijuta; Sullivan, Mike; Toomey, John; Abel, Don; Lippi, Marco; Passerini, Andrea; Frasconi, Paolo; Burley, Stephen K; Rost, Burkhard; Chance, Mark R

    2011-06-01

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  3. Tunable Nanoantennas for Surface Enhanced Infrared Absorption Spectroscopy by Colloidal Lithography and Post-Fabrication Etching

    Chen, Kai; Duy Dao, Thang; Nagao, Tadaaki

    2017-03-01

    We fabricated large-area metallic (Al and Au) nanoantenna arrays on Si substrates using cost-effective colloidal lithography with different micrometer-sized polystyrene spheres. Variation of the sphere size leads to tunable plasmon resonances in the middle infrared (MIR) range. The enhanced near-fields allow us to detect the surface phonon polaritons in the natural SiO2 thin layers. We demonstrated further tuning capability of the resonances by employing dry etching of the Si substrates with the nanoantennas acting as the etching masks. The effective refractive index of the nanoantenna surroundings is efficiently decreased giving rise to blueshifts of the resonances. In addition, partial removal of the Si substrates elevates the nanoantennas from the high-refractive-index substrates making more enhanced near-fields accessible for molecular sensing applications as demonstrated here with surface-enhanced infrared absorption (SEIRA) spectroscopy for a thin polymer film. We also directly compared the plasmonic enhancement from the Al and Au nanoantenna arrays.

  4. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

    2014-11-26

    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

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

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

    2016-03-01

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

  6. New polarisation effects in saturated absorption spectroscopy in the field of counterpropagating light waves

    Brazhnikov, D. V.; Novokreshchenov, V. K.; Ignatovich, S. M.; Taichenachev, A. V.; Yudin, V. I.

    2016-05-01

    The effect of a double structure of saturated absorption resonance in the field of counterpropagating light waves interacting with atomic gas is considered, which was first studied experimentally and theoretically by Vasil'ev et al. [V.V. Vasil'ev et al., J. Exp. Theor. Phys., 112, 770 (2011)]. The effect manifests itself as a new nonlinear resonance formed as a peak in the absorption spectrum of the probe wave. The resonance is observed inside a 'conventional' dip in the spectrum of saturated absorption. Previously, this effect was theoretically described only in the frameworks of the two-level atomic model, i.e., without making allowance for degeneracy of atomic energy levels with respect to the projection of the total angular momentum and for the vector nature of light. We extend the theory of the effect to the case of real atomic systems with degenerate energy levels and arbitrary polarisations of light waves. In particular, on an example of the simple transition Fg = 1 → Fe = 0 we show that polarisation parameters of light waves may significantly affect the contrast of the new effect and the possibility of observing it at all. Conclusions of the work are confirmed both analytically and bnumerically.

  7. System for time-resolved laser absorption spectroscopy and its application to high-power impulse magnetron sputtering

    Adámek, P.; Olejníček, J.; Hubička, Z.; Čada, M.; Kment, Š.; Kohout, M.; Do, H. T.

    2017-02-01

    This paper deals with the development and construction of an apparatus for time-resolved tunable diode laser absorption spectroscopy (LAS) for the diagnostics of pulsed plasma. A detailed description of the extension of a progressive method of laser absorption spectroscopy in continuous regime to a direct triggering method of the time-resolved laser absorption spectroscopy (TR-LAS) is presented. The main advantage of the developed method is its capability to measure the time evolution of the whole absorption profile with a preset time resolution, which can be less than 1 μs. Therefore, the presented method of repetitive sampling applied on LAS in plasma processes is capable of simultaneous measurement of the density and kinetic temperature of selected particles. Its appropriate applications are to periodical processes in technological plasma, namely pulsed plasma discharges. The developed method of TR-LAS was applied to measurements of the temporal evolution of density and kinetic temperature of argon metastable species during high-power impulse magnetron sputtering of titanium and titanium dioxide thin films.

  8. Studies on Negative Refractive Index without Absorption

    Rajapakse, R M; Yelin, S F

    2012-01-01

    Which systems are ideal to obtain negative refraction with no absorption? Electromagnetically induced transparency (EIT) is a method to suppress absorption and make a material transparent to a field of a given frequency. Such a system has been discussed in [1]; however the main limitations for negative refraction introduced are the necessity of resonant electric and magnetic dipole transitions, and the necessity of very dense media. We suggest using frequency translators in a composite system that would provide negative refraction for a range of optical frequencies while attempting to overcome the limitations discussed above. In the process of using frequency translators, we also find composite systems that can be used for refractive index enhancement.

  9. Electronic and lattice structures in SmFeAsO1-xFx probed by x-ray absorption spectroscopy

    Zhang, C. J.; Oyanagi, H.; Sun, Z. H.; Kamihara, Y.; Hosono, H.

    2010-03-01

    Local lattice and electronic structures in the Fe-As layer of SmFeAsO1-xFx superconductors were studied by x-ray absorption spectroscopy, the FeK -edge and the AsK -edge extended x-ray absorption fine-structure, and x-ray absorption near-edge-structure experiments, respectively. Temperature-dependent local lattice distortions were observed in the Fe-As bond mean-square relative displacement of the superconducting samples. A strong coupling of the carrier-induced local lattice distortion (polaron) to the superconducting transition temperature in the oxypnictide superconductors is indicated. The near-edge spectra showed systematic temperature-dependent energy shifts, which indicate an intralayer electron redistribution from Fed states to Asp states due to orbital-selective band filling at low temperatures.

  10. Bifunctional Ce(1-x)Eu(x)O2 (0 ≤x≤ 0.3) nanoparticles for photoluminescence and photocatalyst applications: an X-ray absorption spectroscopy study.

    Sharma, Aditya; Varshney, Mayora; Park, Jaehun; Ha, Tae Kyun; Chae, Keun Hwa; Shin, Hyun Joon

    2015-11-28

    Ce1-xEuxO2 (0 ≤x≤ 0.3) nanoparticles (NPs) were synthesized by the chemical precipitation method. The microstructures and morphology were characterized by synchrotron X-ray diffraction and high resolution transmission electron microscopy. X-ray absorption near edge structure (XANES) spectra at the Eu M5,4-edge and atomic-multiplet calculations revealed that Eu(3+) was predominantly present in the CeO2 lattice and Eu(2+) was negligibly present within the entire doping range. The detailed analysis of the Ce M5,4-edge and the O K-edge has shown strong dependence of the Ce(3+)/Ce(4+) ratio and oxygen vacancy with Eu content. Extended X-ray absorption fine structure (EXAFS) spectra at the Ce K-edge, along with theoretical fitting, have shown systematic variation in the coordination number, bond length and Debye-Waller factor with Eu doping. A blue shift in the absorption edge was observed which implies a net increase in the charge transfer gap between the O 2p and Ce 4f bands due to the increased number of Ce(3+) ions in the Eu doped samples. The excitation and emission spectra of pure CeO2 NPs did not show any photoluminescence (PL) characteristic; however, Ce1-xEuxO2 (x = 0.1-0.3) NPs showed significant improvements in the 4f-4f, (5)D0-(7)F2 and (5)D0-(7)F1 transitions induced luminescence properties. Eu doping has two major effects on the electronic structure and optical properties of CeO2 NPs: the first, at an Eu content of 10 mol%, is the formation of Ce(4+)-O-Eu(3+) networks, i.e., Eu(3+) ions substitute the Ce(4+) ions and introduce oxygen vacancies and Ce(3+) ions in the host lattice, which favors the (5)D0-(7)F2 induced PL properties. The other, at an Eu doping over 10 mol%, is the formation of both Ce(4+)-O-Eu(3+) and Ce(3+)-O-Eu(3+), i.e., Eu(3+) ions not only take substitutional sites of Ce(4+) ions but also replace a fraction of Ce(3+) ions in the CeO2 lattice which favors (5)D0-(7)F1 induced PL properties. As an application of CeO2 NPs towards the

  11. The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

    Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

    2016-05-01

    Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

  12. Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

    Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

    2005-07-01

    Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

  13. Laser-induced absorption and fluorescence studies of photochromic Schiff bases

    Kownacki, K.; Mordzinski, A.; Wilbrandt, R.

    1994-01-01

    Three photochromic Schiff bases: N-salicylideneaniline (SA), N-salicylidene-1-naphthylamine (SN), and N,N-bis-(salicylidene)-p-phenylenediamine (Bsp), were studied in acetonitrile by means of steady-state and time-resolved absorption and fluorescence spectroscopy, as well as semiempirical quantum...... chemical calculations. In all these molecules, the transient absorption and two-step laser-induced fluorescence spectra of long-lived transients are remarkably similar. The photochromic species is tentatively assigned to the non-hydrogen bonded form of the proton transfer reaction product...

  14. X-ray absorption spectroscopy systematics at the tungsten L-edge.

    Jayarathne, Upul; Chandrasekaran, Perumalreddy; Greene, Angelique F; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Donahue, James P

    2014-08-18

    A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W(0)(PMe3)6], [W(II)Cl2(PMePh2)4], [W(III)Cl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [W(IV)Cl4(PMePh2)2], [W(V)(NPh)Cl3(PMe3)2], and [W(VI)Cl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W(IV)(mdt)2(CO)2] and [W(IV)(mdt)2(CN)2](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W(IV) species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate

  15. Vacuum-UV spectroscopy of interstellar ice analogs. I. Absorption cross-sections of polar-ice molecules

    Cruz-Diaz, G. A.; Muñoz Caro, G. M.; Chen, Y.-J.; Yih, T.-S.

    2014-02-01

    Context. The vacuum-UV (VUV) absorption cross sections of most molecular solids present in interstellar ice mantles with the exception of H2O, NH3, and CO2 have not been reported yet. Models of ice photoprocessing depend on the VUV absorption cross section of the ice to estimate the penetration depth and radiation dose, and in the past, gas phase cross section values were used as an approximation. Aims: We aim to estimate the VUV absorption cross section of molecular ice components. Methods: Pure ices composed of CO, H2O, CH3OH, NH3, or H2S were deposited at 8 K. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave-discharged hydrogen flow lamp. Results: We provide VUV absorption cross sections of the reported molecular ices. Our results agree with those previously reported for H2O and NH3 ices. Vacuum-UV absorption cross section of CH3OH, CO, and H2S in solid phase are reported for the first time. H2S presents the highest absorption in the 120-160 nm range. Conclusions: Our method allows fast and readily available VUV spectroscopy of ices without the need to use a synchrotron beamline. We found that the ice absorption cross sections can be very different from the gas-phase values, and therefore, our data will significantly improve models that simulate the VUV photoprocessing and photodesorption of ice mantles. Photodesorption rates of pure ices, expressed in molecules per absorbed photon, can be derived from our data. Data can be found at http://ghosst.osug.fr/

  16. Electronic structure of barium strontium titanate by soft-x-ray absorption spectroscopy

    Uehara, Y. [Mitsubishi Electric Co., Hyogo (Japan); Underwood, J.H.; Gullikson, E.M.; Perera, R.C.C. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    Perovskite-type titanates, such as Strontium Titanate (STO), Barium Titanate (BTO), and Lead Titanate (PTO) have been widely studied because they show good electric and optical properties. In recent years, thin films of Barium Strontium Titanate (BST) have been paid much attention as dielectrics of dynamic random access memory (DRAM) capacitors. BST is a better insulator with a higher dielectric constant than STO and can be controlled in a paraelectric phase with an appropriate ratio of Ba/Sr composition, however, few studies have been done on the electronic structure of the material. Studies of the electronic structure of such materials can be beneficial, both for fundamental physics research and for improving technological applications. BTO is a famous ferroelectric material with a tetragonal structure, in which Ti and Ba atoms are slightly displaced from the lattice points. On the other hand, BST keeps a paraelectric phase, which means that the atoms are still at the cubic lattice points. It should be of great interest to see how this difference of the local structure around Ti atoms between BTO and BST effects the electronic structure of these two materials. In this report, the authors present the Ti L{sub 2,3} absorption spectra of STO, BTO, and BST measured with very high accuracy in energy of the absorption features.

  17. Plutonium in monazite and brabantite: Diffuse reflectance spectroscopy study

    Zhang Yingjie [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia)], E-mail: yzx@ansto.gov.au; Vance, Eric R. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia)

    2008-04-30

    The valence states of plutonium (Pu) in monazite and brabantite have been studied by using diffuse reflectance spectroscopy. In the absence of charge compensators, Pu exists mainly as trivalent ions in air-fired monazites and only trivalent ions in argon-fired monazites. However, with added Ca{sup 2+}/Pb{sup 2+} as charge compensators Pu can exist as tetravalent ions. Published data on absorption spectra of both trivalent and tetravalent Pu ions in the monazite structure have been extended to the mid near infrared region (4000 cm{sup -1})

  18. Measuring spin diffusion of electrons in bulk n-GaAs using circularly dichromatic absorption difference spectroscopy of spin gratings

    Yu, Hua-Liang; Zhang, Xiu-Min; Wang, Peng-Fei; Ni, Hai-Qiao; Niu, Zhi-Chuan; Lai, Tianshu

    2009-05-01

    Circular dichromatic absorption difference spectroscopy is developed to measure the spin diffusion dynamics of electrons in bulk n-GaAs. This spectroscopy has higher detection sensitivity over homodyne detection of spin-grating-diffracted signal. A model to describe circular dichromatic absorption difference signal is derived and used to fit experimental signal to retrieve decaying rate of spin gratings. A spin diffusion constant of Ds=201±25 cm2/s for bulk n-GaAs has been measured at room temperature using this technique and is close to electron diffusion constant (Dc), which is much different from the case in GaAs quantum wells where Ds is markedly less than Dc.

  19. Direct correlation of charge transfer absorption with molecular donor:acceptor interfacial area via photothermal deflection spectroscopy

    Domingo, Ester

    2015-04-09

    We show that the Charge Transfer (CT) absorption signal in bulk-heterojunction (BHJ) solar cell blends, measured by photothermal deflection spectroscopy (PDS), is directly proportional to the density of molecular donor/acceptor interfaces. Since the optical transitions from ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer-fullerene interface. The latter is ~100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment (0.3 D) and the electronic coupling between ground state and CT state to be on the order of 30 meV.

  20. Performance assessment and signal processing for range-integrated concentration measurement of gas species using supercontinuum absorption spectroscopy.

    Dobroc, Alexandre; Cézard, Nicolas

    2012-12-10

    In this paper, we propose signal-processing tools adapted to supercontinuum absorption spectroscopy, in order to predict the precision of gas species concentration estimation. These tools are based on Cramer-Rao bounds computations. A baseline-insensitive concentration estimation algorithm is proposed. These calculations are validated by statistical tests on simulated supercontinuum signals as well as experimental data using a near-infrared supercontinuum laser and a grating spectrometer.

  1. X-ray absorption fine structure (XAFS) studies of cobalt silicide thin films

    Naftel, S.J.; Coulthard, I.; Hu, Y.; Sham, T.K.; Zinke-Allmang, M. [Univ. of Western Ontario, London, Ontario (Canada)

    1998-12-31

    Cobalt silicide thin films, prepared on Si(100) wafers, have been studied by X-ray absorption near edge structures (XANES) at the Si K-, L{sub 2,3}- and Co K-edges utilizing both total electron (TEY) and fluorescence yield (FLY) detection as well as extended X-ray absorption fine structure (EXAFS) at the Co K-edge. Samples made using DC sputter deposition on clean Si surfaces and MBE were studied along with a bulk CoSi{sub 2} sample. XANES and EXAFS provide information about the electronic structure and morphology of the films. It was found that the films studied have essentially the same structure as bulk CoSi{sub 2}. Both the spectroscopy and materials characterization aspects of XAFS (X-ray absorption fine structures) are discussed.

  2. Differential optical absorption spectroscopy (DOAS and air mass factor concept for a multiply scattering vertically inhomogeneous medium: theoretical consideration

    V. V. Rozanov

    2010-06-01

    Full Text Available The Differential Optical Absorption Spectroscopy (DOAS technique is widely used to retrieve amounts of atmospheric species from measurements of the direct solar light transmitted through the Earth's atmosphere as well as of the solar light scattered in the atmosphere or reflected from the Earth's surface. For the transmitted direct solar light the theoretical basis of the DOAS technique represented by the Beer-Lambert law is well studied. In contrast, scarcely investigated is the theoretical basis and validity range of the DOAS method for those cases where the contribution of the multiple scattering processes is not negligible. Our study is intended to fill this gap by means of a theoretical investigation of the applicability of the DOAS technique for the retrieval of amounts of atmospheric species from observations of the scattered solar light with a non-negligible contribution of the multiple scattering.

    Starting from the expansion of the intensity logarithm in the functional Taylor series we formulate the general form of the DOAS equation. The thereby introduced variational derivative of the intensity logarithm with respect to the variation of the gaseous absorption coefficient, which is often referred to as the weighting function, is demonstrated to be closely related to the air mass factor. Employing some approximations we show that the general DOAS equation can be rewritten in the form of the weighting function (WFDOAS, the modified (MDOAS, and the standard DOAS equations. For each of these forms a specific equation for the air mass factor follows which, in general, is not suitable for other forms of the DOAS equation. Furthermore, the validity range of the standard DOAS equation is quantitatively investigated using a suggested criterion of a weak absorption.

    The results presented in this study are intended to provide a basis for a better understanding of the applicability range of different forms of the DOAS equation as

  3. Investigation on an evanescent wave fiber-optic absorption sensor based on fiber loop cavity ring-down spectroscopy

    Jiang, Meng; Zhang, Weigang; Zhang, Qi; Liu, Yaping; Liu, Bo

    2010-01-01

    An improved ring-down measurement principle for optical waveguides is presented. Fiber loop ring-down spectroscopy allows for measurement of minute optical losses in high-finesse fiber-optic cavities and immunity to the fluctuation of laser source. The evanescent wave absorption losses dependent on the absorption and the refractive index of ambient solution have been theoretically analyzed. The complex refractive index is introduced into our model and extinction coefficient can be calculated accurately through finite element analysis by setting the boundaries of the fiber and the ambient conditions. Using this method, the refractive index of environment can be taken into consideration. Our principle is validated by the highly-sensitive measurement of evanescent wave absorption loss. By chemically processing the surface of sensing segment along an extending ring-down cavity, the concentration of small volume Diethyl Sulphoxide solution where the etched fiber immersed into has been successfully measured and discussed.

  4. Time- and space-resolved X-ray absorption spectroscopy of aluminum irradiated by a subpicosecond high-power laser

    Tzortzakis, S.; Audebert, P.; Renaudin, P.; Bastiani-Ceccotti, S.; Geindre, J. P.; Chenais-Popovics, C.; Nagels, V.; Gary, S.; Shepherd, R.; Girard, F.; Matsushima, I.; Peyrusse, O.; Gauthier, J.-C.

    2006-05-01

    The ionization and recombination dynamics of transient aluminum plasmas was measured using point projection K-shell absorption spectroscopy. An aluminum plasma was produced with a subpicosecond beam of the 100-TW laser at the LULI facility and probed at different times with a picosecond X-ray backlighter created with a synchronized subpicosecond laser beam. Fourier-Domain-Interferometry (FDI) was used to measure the electron temperature at the peak of the heating laser pulse. Absorption X-ray spectra at early times are characteristic of a dense and rather homogeneous plasma, with limited longitudinal gradients as shown by hydrodynamic simulations. The shift of the Al K-edge was measured in the cold dense plasma located at the edge of the heated plasma. From the 1s 2p absorption spectra, the average ionization was measured as a function of time and was also modeled with a collisional-radiative atomic physics code coupled with hydrodynamic simulations.

  5. Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy

    Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew; Chen, Jun; Zhuo, Zengqing; Chen, Yanxue; Yan, Shishen; Pan, Feng; Hussain, Zahid; Yang, Wanli

    2016-10-01

    Most battery positive electrodes operate with a 3d transition-metal (TM) reaction centre. A direct and quantitative probe of the TM states upon electrochemical cycling is valuable for understanding the detailed cycling mechanism and charge diffusion in the electrodes, which is related with many practical parameters of a battery. This review includes a comprehensive summary of our recent demonstrations of five different types of quantitative analysis of the TM states in battery electrodes based on soft x-ray absorption spectroscopy and multiplet calculations. In LiFePO4, a system of a well-known two-phase transformation type, the TM redox could be strictly determined through a simple linear combination of the two end-members. In Mn-based compounds, the Mn states could also be quantitatively evaluated, but a set of reference spectra with all the three possible Mn valences needs to be deliberately selected and considered in the fitting. Although the fluorescence signals suffer the self-absorption distortion, the multiplet calculations could consider the distortion effect, which allows a quantitative determination of the overall Ni oxidation state in the bulk. With the aid of multiplet calculations, one could also achieve a quasi-quantitative analysis of the Co redox evolution in LiCoO2 based on the energy position of the spectroscopic peak. The benefit of multiplet calculations is more important for studying electrode materials with TMs of mixed spin states, as exemplified by the quantitative analysis of the mixed spin Na2-x Fe2(CN)6 system. At the end, we showcase that such quantitative analysis could provide valuable information for optimizing the electrochemical performance of Na0.44MnO2 electrodes for Na-ion batteries. The methodology summarized in this review could be extended to other energy application systems with TM redox centre for detailed analysis, for example, fuel cell and catalytic materials.

  6. Multiple Absorption-Line Spectroscopy of the Intergalactic Medium. I. Model

    Yao, Yangsen; Danforth, Charles W; Keeney, Brian A; Stocke, John T

    2011-01-01

    We present a physically-based absorption-line model for the spectroscopic study of the intergalactic medium (IGM). This model adopts results from Cloudy simulations and theoretical calculations by Gnat and Sternberg (2007) to examine the resulting observational signatures of the absorbing gas with the following ionization scenarios: collisional ionization equilibrium (CIE), photoionization equilibrium, hybrid (photo- plus collisional ionization), and non-equilibrium cooling. As a demonstration, we apply this model to new observations made with the Cosmic Origins Spectrograph aboard the Hubble Space Telescope of the IGM absorbers at z~0.1877 along the 1ES 1553+113 sight line. We identify Ly alpha, C III, O VI, and N V absorption lines with two distinct velocity components (blue at z_b=0.18757; red at z_r=0.18772) separated by Delta(cz)/(1+z)~38 km/s. Joint analyses of these lines indicate that none of the examined ionization scenarios can be applied with confidence to the blue velocity component, although phot...

  7. Time-resolved X-ray absorption spectroscopy for the study of solid state reactions: synthesis of nanocrystalline barium titanate and thermal decomposition of ammonium hexachlorometallate compounds; Zeitaufgeloeste Roentgenabsorptionspektroskopie zur Untersuchung von Festkoerperreaktionen: Synthese von nanokristallinem Bariumtitanat und thermische Zersetzung von Ammoniumhexachlorometallat-Verbindungen

    Rumpf, H.

    2001-07-01

    This report presents investigations on the mechanism of two different types of solid-state reactions: At first, barium titanate nanopowders were prepared through a combined polymerization and pyrolysis of a metallo-organic precursor. The mean particle size d{sub m} could be adjusted by choosing appropriate reaction temperatures and tempering atmospheres. In the present in situ study of this particular solid-phase reaction, X-ray absorption near edge structure (XANES) spectroscopy at the Ti K and Ba L{sub 3}-edges was applied in the preparation route of BaTiO{sub 3} nanopowders. A pronounced distortion of the lattice symmetry was found to occur in very fine BaTiO{sub 3} nanopowders (d{sub m} < 20 nm). Secondly, in situ XANES investigations were carried out at the Cl K, Pd L{sub 3}, Rh L{sub 3}, and Pt L{sub 3}-edges to study the mechanism of the thermal decomposition of ammonium hexachlorometallates. The results exceed structural information obtained by in situ X-ray diffraction methods and thermal analysis. Feff8 multiple scattering simulations have been carried out to disclose new intermediate phases of unknown reference compounds. (orig.)

  8. Soft x-ray irradiation effects of Li₂O₂, Li₂CO₃ and Li₂O revealed by absorption spectroscopy.

    Ruimin Qiao

    Full Text Available Li(2O(2, Li(2CO(3, and Li(2O are three critical compounds in lithium-air and lithium-ion energy storage systems. Extensive measurements have been carried out to study the chemical species and their evolutions at difference stages of the device operation. While x-ray spectroscopy has been demonstrated to be one of the most powerful tools for such purpose, no systematic study on the irradiation effects have been reported. Here we carry out extensive time, position, and irradiation dependent Li K-edge soft x-ray absorption spectroscopy on these compounds with so far the best energy resolution. The ultra-high resolution in the current study allows the features in the absorption spectra to be well-resolved. The spectral lineshape thus serves as the fingerprints of these compounds, enabling the tracking of their evolution under x-ray irradiation. We found that both Li(2O(2 and Li(2CO(3 evidently evolve towards Li(2O under the soft x-ray irradiation with Li(2CO(3 exhibiting a surprisingly higher sensitivity to x-rays than Li(2O(2. On the other hand, Li(2O remains the most stable compound despite experiencing substantial irradiation dose. We thus conclude that high resolution soft x-ray spectroscopy could unambiguously fingerprint different chemical species, but special cautions on irradiation effects would be needed in performing the experiments and interpreting the data properly.

  9. A new calibration system for lightweight, compact and mobile Cavity-Enhanced Differential Optical Absorption Spectroscopy instruments

    Zielcke, Johannes; Horbanski, Martin; Pöhler, Denis; Frieß, Udo; Platt, Ulrich

    2013-04-01

    Absorption Spectroscopy has been employed for several decades now to study the earth's atmosphere. While the focus has been on remote sensing for a long time, lately there has been a renewed interest in in-situ methods, as point measurements allow an easier interpretation for highly inhomogeneous distributions of gases of interest compared to the integration approach of most remote sensing methods. One comparatively new method offering both advantages of in-situ measurements as well as being contactless is open-path Cavity-Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS). Broadband open-path CE-DOAS instruments have been used for ten years now, and in the meantime allow the measurement of numerous atmospheric trace gases (e.g. NO2, NO3, IO, CHOCHO, HCHO). While those instruments were bulky and not very mobile at first, recent developments resulted in relatively lightweight (< 30 kg) instruments with a relatively low power consumption allowing mobile open-path measurements at remote field locations. An important operational issue has been the path length calibration in the field, necessary for the determination of the concentration of measured gases. Until now, often calibration gases were used with different scattering properties than air or known concentrations. However this methods has several major shortcomings, being rather inconvenient and cumbersome in the field with the need for compressed gas cylinders, as well as time consuming, preventing a quick check of the state of the instrument in the field after changing measurement locations. Here we present a new wavelength-resolved method for broadband CE-DOAS path length calibration. A small, custom made ring-down system is employed with a pulsed LED as light source. The wavelength is then resolved by tilting a narrow band interference filter. The system not only allows quick, automated path length calibrations without physical interaction on the instrument, but also saves weight, space and the

  10. Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy

    Santomauro, Fabio G.; Grilj, Jakob; Mewes, Lars; Nedelcu, Georgian; Yakunin, Sergii; Rossi, Thomas; Capano, Gloria; Al Haddad, André; Budarz, James; Kinschel, Dominik; Ferreira, Dario S.; Rossi, Giacomo; Gutierrez Tovar, Mario; Grolimund, Daniel; Samson, Valerie; Nachtegaal, Maarten; Smolentsev, Grigory; Kovalenko, Maksym V.; Chergui, Majed

    2016-01-01

    We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge, and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes is observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. This first, time-resolved element-specific study of perovskites helps understand the rather modest charge carrier mobilities in these materials. PMID:28083541

  11. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    Cinco, Roehl M. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH2OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees ± 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and

  12. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    Cinco, Roehl M.

    1999-12-16

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and glutathione show distinct

  13. Magnetic-dipolar-mode Fano resonances for microwave spectroscopy of high absorption matter

    Vaisman, G; Shavit, R

    2015-01-01

    Study of interaction between high absorption matter and microwave radiated energy is a subject of great importance. Especially, this concerns microwave spectroscopic characterization of biological liquids. Use of effective testing methods to obtain information about physical properties of different liquids on the molecular level is one of the most important problems in biophysics. However, the standard methods based on the microwave resonant techniques are not sufficiently suitable for biological liquids because the resonance peak in a resonator with high-loss liquids is so broad that the material parameters cannot be measured correctly. Although molecular vibrations of biomolecules may have microwave frequencies, it is not thought that such resonant coupling is significant due to their low energy compared with thermal energy and the strongly dampening aqueous environment. This paper presents an innovative microwave sensing technique for different types of lossy materials, including biological liquids. The te...

  14. UV-vis absorption spectroscopy and multivariate analysis as a method to discriminate tequila

    Barbosa-García, O.; Ramos-Ortíz, G.; Maldonado, J. L.; Pichardo-Molina, J. L.; Meneses-Nava, M. A.; Landgrave, J. E. A.; Cervantes-Martínez, J.

    2007-01-01

    Based on the UV-vis absorption spectra of commercially bottled tequilas, and with the aid of multivariate analysis, it is proved that different brands of white tequila can be identified from such spectra, and that 100% agave and mixed tequilas can be discriminated as well. Our study was done with 60 tequilas, 58 of them purchased at liquor stores in various Mexican cities, and two directly acquired from a distillery. All the tequilas were of the "white" type, that is, no aged spirits were considered. For the purposes of discrimination and quality control of tequilas, the spectroscopic method that we present here offers an attractive alternative to the traditional methods, like gas chromatography, which is expensive and time-consuming.

  15. Vacuum-UV spectroscopy of interstellar ice analogs. I. Absorption cross-sections of polar-ice molecules

    Cruz-Diaz, G A; Chen, Y -J; Yih, T -S

    2014-01-01

    The VUV absorption cross sections of most molecular solids present in interstellar ice mantles with the exception of H2O, NH3, and CO2 have not been reported yet. Models of ice photoprocessing depend on the VUV absorption cross section of the ice to estimate the penetration depth and radiation dose, and in the past, gas phase cross section values were used as an approximation. We aim to estimate the VUV absorption cross section of molecular ice components. Pure ices composed of CO, H2O, CH3OH, NH3, or H2S were deposited at 8 K. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave-discharged hydrogen flow lamp. We provide VUV absorption cross sections of the reported molecular ices. Our results agree with those previously reported for H2O and NH3 ices. Vacuum-UV absorption cross section of CH3OH, CO, and H2S in solid phase are reported for the first...

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

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

    2006-04-01

    Acrolein (C(3)H(4)O) 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.

  17. Lattice Studies of Hyperon Spectroscopy

    Richards, David G. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

    2016-04-01

    I describe recent progress at studying the spectrum of hadrons containing the strange quark through lattice QCD calculations. I emphasise in particular the richness of the spectrum revealed by lattice studies, with a spectrum of states at least as rich as that of the quark model. I conclude by prospects for future calculations, including in particular the determination of the decay amplitudes for the excited states.

  18. New Homogeneous Standards by Atomic Layer Deposition for Synchrotron X-ray Fluorescence and Absorption Spectroscopies.

    Butterworth, A.L.; Becker, N.; Gainsforth, Z.; Lanzirotti, A.; Newville, M.; Proslier, T.; Stodolna, J.; Sutton, S.; Tyliszczak, T.; Westphal, A.J.; Zasadzinski, J. (UCB)

    2012-03-13

    Quantification of synchrotron XRF analyses is typically done through comparisons with measurements on the NIST SRM 1832/1833 thin film standards. Unfortunately, these standards are inhomogeneous on small scales at the tens of percent level. We are synthesizing new homogeneous multilayer standards using the Atomic Layer Deposition technique and characterizing them using multiple analytical methods, including ellipsometry, Rutherford Back Scattering at Evans Analytical, Synchrotron X-ray Fluorescence (SXRF) at Advanced Photon Source (APS) Beamline 13-ID, Synchrotron X-ray Absorption Spectroscopy (XAS) at Advanced Light Source (ALS) Beamlines 11.0.2 and 5.3.2.1 and by electron microscopy techniques. Our motivation for developing much-needed cross-calibration of synchrotron techniques is borne from coordinated analyses of particles captured in the aerogel of the NASA Stardust Interstellar Dust Collector (SIDC). The Stardust Interstellar Dust Preliminary Examination (ISPE) team have characterized three sub-nanogram, {approx}1{micro}m-sized fragments considered as candidates to be the first contemporary interstellar dust ever collected, based on their chemistries and trajectories. The candidates were analyzed in small wedges of aerogel in which they were extracted from the larger collector, using high sensitivity, high spatial resolution >3 keV synchrotron x-ray fluorescence spectroscopy (SXRF) and <2 keV synchrotron x-ray transmission microscopy (STXM) during Stardust ISPE. The ISPE synchrotron techniques have complementary capabilities. Hard X-ray SXRF is sensitive to sub-fg mass of elements Z {ge} 20 (calcium) and has a spatial resolution as low as 90nm. X-ray Diffraction data were collected simultaneously with SXRF data. Soft X-ray STXM at ALS beamline 11.0.2 can detect fg-mass of most elements, including cosmochemically important oxygen, magnesium, aluminum and silicon, which are invisible to SXRF in this application. ALS beamline 11.0.2 has spatial resolution

  19. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  20. Composition and structure of Pt chloride complexes in hydrothermal solutions, according to X-ray absorption spectroscopy

    Tagirov, B. R.; Trigub, A. L.; Selivanov, P. V.; Koroleva, L. A.

    2017-03-01

    The local atomic environment of Pt in chloride solutions is studied at 25 and 300-350°C via X-ray absorption spectroscopy. A comparison of the Pt L 3-edge XANES spectra for aqueous chloride solutions and reference compounds (K2PtCl4 and K2PtCl6) shows that platinum is in oxidation state +2 at all temperatures, and the complex composition remains unchanged in the experimental range of temperatures (25-350°C) and solution compositions ( m(Cltot) > 0.4 mol kg-1 of H2O). Based on EXAFS spectral analysis, the composition of the complex being dominant in chloride solutions is found to be PtCl4 2- with interatomic Pt-Cl distances of 2.31 ± 0.01 Å, regardless of the temperature. It is concluded that the local environments of Pt and Pd in hydrothermal solutions are similar, and the main form of transfer for these metals is a square-planar complex with four Cl ligands and identical interatomic distances.