WorldWideScience

Sample records for broadband time-resolved spectroscopy

  1. Sensitive, time-resolved, broadband spectroscopy of single transient processes

    Science.gov (United States)

    Fjodorow, Peter; Baev, Ivan; Hellmig, Ortwin; Sengstock, Klaus; Baev, Valery M.

    2015-09-01

    Intracavity absorption spectroscopy with a broadband Er3+-doped fiber laser is applied to time-resolved measurements of transient gain and absorption in electrically excited Xe and Kr plasmas. The achieved time resolution for broadband spectral recording of a single process is 25 µs. For pulsed-periodic processes, the time resolution is limited by the laser pulse duration, which is set here to 3 µs. This pulse duration also predefines the effective absorption path length, which amounts to 900 m. The presented technique can be applied to multicomponent analysis of single transient processes such as shock tube experiments, pulse detonation engines, or explosives.

  2. Broad-band time-resolved near infrared spectroscopy in the TJ-II stellarator

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, M.C.; Pastor, I.; Cal, E. de la; McCarthy, K.J. [Laboratorio Nacional de Fusion, CIEMAT, Madrid (Spain); Diaz, D. [Universidad Autonoma de Madrid, Dept Quimica Fisica Aplicada, Madrid (Spain)

    2014-11-15

    First experimental results on broad-band, time-resolved Near Infrared (NIR;here loosely defined as covering from 750 to 1650 nm) passive spectroscopy using a high sensitivity InGaAs detector are reported for the TJ-II Stellarator. Experimental set-up is described together with its main characteristics, the most remarkable ones being its enhanced NIR response, broadband spectrum acquisition in a single shot, and time-resolved measurements with up to 1.8 kHz spectral rate. Prospects for future work and more extended physics studies in this newly open spectral region in TJ-II are discussed. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  3. Broadband THz waveguiding and high-precision broadband time-resolved spectroscopy

    DEFF Research Database (Denmark)

    Cooke, David; Iwaszczuk, Krzysztof; Nielsen, Kristian; Bang, Ole; Jepsen, Peter Uhd

    2009-01-01

    , particularly in spectroscopic applications where tight confinement of the THz field is required. We further demonstrate a new spectroscopic technique for ultrafast time-resolved THz time-domain spectroscopy which simultaneously acquires both reference and sample data. By using this scheme we show that the...... influence of fluctuations on the laser parameters during data acquisition can be minimized, and highly reproducible quantitative data can be recorded and extracted in a very efficient manner. This technique may become especially important in the high THz range, where phase noise becomes critical for the...

  4. Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. TIME-RESOLVED VIBRATIONAL SPECTROSCOPY

    Energy Technology Data Exchange (ETDEWEB)

    Andrei Tokmakoff, MIT (Conference Chair); Paul Champion, Northeastern University; Edwin J. Heilweil, NIST; Keith A. Nelson, MIT; Larry Ziegler, Boston University

    2009-05-14

    This document contains the Proceedings from the 14th International Conference on Time-Resolved Vibrational Spectroscopy, which was held in Meredith, NH from May 9-14, 2009. The study of molecular dynamics in chemical reaction and biological processes using time-resolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE’s Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation of reactive intermediates in radiation chemistry. In addition, time-resolved spectroscopy is central to all five of DOE’s grand challenges for fundamental energy science. The Time-Resolved Vibrational Spectroscopy conference is organized biennially to bring the leaders in this field from around the globe together with young scientists to discuss the most recent scientific and technological advances. The latest technology in ultrafast infrared, Raman, and terahertz spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.

  6. Time-resolved fluorescence spectroscopy

    International Nuclear Information System (INIS)

    This article addresses the evolution in time of light emitted by a molecular system after a brief photo-excitation. The authors first describe fluorescence from a photo-physical point of view and discuss the characterization of the excited state. Then, they explain some basic notions related to fluorescence characterization (lifetime and decays, quantum efficiency, so on). They present the different experimental methods and techniques currently used to study time-resolved fluorescence. They discuss basic notions of time resolution and spectral reconstruction. They briefly present some conventional methods: intensified Ccd cameras, photo-multipliers and photodiodes associated with a fast oscilloscope, and phase modulation. Other methods and techniques are more precisely presented: time-correlated single photon counting (principle, examples, and fluorescence lifetime imagery), streak camera (principle, examples), and optical methods like the Kerr optical effect (principle and examples) and fluorescence up-conversion (principle and theoretical considerations, examples of application)

  7. Time Resolved Broadband Terahertz Relaxation Dynamics of Electron in Water

    DEFF Research Database (Denmark)

    Wang, Tianwu; Iwaszczuk, Krzysztof; Cooke, David G.;

    We investigated the transient response of the solvated electron in water ejected by photodetachment from potassium ferrocyanide using time resolved terahertz spectroscopy (TSTS). Ultrabroadband THz transients are generated and detected by a two-color femtosecond-induced air plasma and air biased...... coherent detection, respectively. We find that the measured frequency dependent conductivity can be well described by a Drude-Smith model, supplemented by a Lorentz model oscillating near 5 THz....

  8. Application of a mode-locked fiber laser for highly time resolved broadband absorption spectroscopy and laser-assisted breakdown on micro-plasmas

    International Nuclear Information System (INIS)

    Absorption spectroscopy is known to be a powerful tool to gain spatially and temporally resolved information on excited and reactive species in a plasma discharge. Furthermore, the interaction of the discharge with short intense laser pulses can trigger the ignition and the transition into other transient states of the plasma. In this context laser-assisted ‘pump-probe’ experiments involving simultaneously generated supercontinuum radiation yield highly temporally resolved and spatially well-defined information on the transient phenomena. In this paper we demonstrate the possibility for ‘pump-probe’ experiments by initiating breakdown on a picosecond time scale (‘pump’) with a high-power beam and measuring the broadband absorption with the simultaneously provided supercontinuum (‘probe’). Since both pulses are generated from the same mode-locked master oscillator, they have a strong level of synchronization. (paper)

  9. Time-resolved orbital angular momentum spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Noyan, Mehmet A.; Kikkawa, James M. [Department of Physics and Astronomy, The University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)

    2015-07-20

    We introduce pump-probe magneto-orbital spectroscopy, wherein Laguerre-Gauss optical pump pulses impart orbital angular momentum to the electronic states of a material and subsequent dynamics are studied with 100 fs time resolution. The excitation uses vortex modes that distribute angular momentum over a macroscopic area determined by the spot size, and the optical probe studies the chiral imbalance of vortex modes reflected off the sample. First observations in bulk GaAs yield transients that evolve on time scales distinctly different from population and spin relaxation, as expected, but with surprisingly large lifetimes.

  10. Time-resolved orbital angular momentum spectroscopy

    International Nuclear Information System (INIS)

    We introduce pump-probe magneto-orbital spectroscopy, wherein Laguerre-Gauss optical pump pulses impart orbital angular momentum to the electronic states of a material and subsequent dynamics are studied with 100 fs time resolution. The excitation uses vortex modes that distribute angular momentum over a macroscopic area determined by the spot size, and the optical probe studies the chiral imbalance of vortex modes reflected off the sample. First observations in bulk GaAs yield transients that evolve on time scales distinctly different from population and spin relaxation, as expected, but with surprisingly large lifetimes

  11. Seventh international conference on time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, R.B.; Martinez, M.A.D.; Shreve, A.; Woodruff, W.H. [comps.

    1997-04-01

    The International Conference on Time-Resolved Vibrational Spectroscopy (TRVS) is widely recognized as the major international forum for the discussion of advances in this rapidly growing field. The 1995 conference was the seventh in a series that began at Lake Placid, New York, 1982. Santa Fe, New Mexico, was the site of the Seventh International Conference on Time-Resolved Vibrational Spectroscopy, held from June 11 to 16, 1995. TRVS-7 was attended by 157 participants from 16 countries and 85 institutions, and research ranging across the full breadth of the field of time-resolved vibrational spectroscopy was presented. Advances in both experimental capabilities for time-resolved vibrational measurements and in theoretical descriptions of time-resolved vibrational methods continue to occur, and several sessions of the conference were devoted to discussion of these advances and the associated new directions in TRVS. Continuing the interdisciplinary tradition of the TRVS meetings, applications of time-resolved vibrational methods to problems in physics, biology, materials science, and chemistry comprised a large portion of the papers presented at the conference.

  12. Time-resolved terahertz spectroscopy of black silicon

    DEFF Research Database (Denmark)

    Porte, Henrik; Turchinovich, Dmitry; Jepsen, Peter Uhd;

    2010-01-01

    The ultrafast photoconductivity dynamics of black silicon is measured by time-resolved terahertz spectroscopy. Black silicon is produced by laser annealing of an a-Si:H film. We show that the decay time of the photoconductivity depends on the annealing method and fluence used in the production...

  13. Time-resolved study of microorganisms by Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Samek, Ota; Hároniková, A.; Obruča, S.; Bernatová, Silvie; Ježek, Jan; Šiler, Martin; Mlynariková, K.; Zemánek, Pavel

    Bellingham: SPIE, 2015, 953703:1-5. ISBN 9781628417029. ISSN 1605-7422. [Clinical and Biomedical Spectroscopy and Imaging /4./. Munich (DE), 22.06.2015-24.06.2015] R&D Projects: GA MŠk(CZ) LO1212; GA MŠk ED0017/01/01; GA ČR(CZ) GA15-20645S Institutional support: RVO:68081731 Keywords : raman spectroscopy * time-resolved study * red yeast * Cupriavidus necator H16 Subject RIV: BH - Optics, Masers, Lasers

  14. Time-resolved THz spectroscopy in a parallel plate waveguide

    DEFF Research Database (Denmark)

    Cooke, David; Jepsen, Peter Uhd

    2009-01-01

    We demonstrate time-resolved terahertz spectroscopy inside a novel parallel plate waveguide where one of the metallic plates is replaced by a transparent conducting oxide. Considerable improvements to the waveguide loss coefficient are shown, with a power absorption coefficient of 4cm-1 at 0.5 TH....... The time resolution of the technique is shown to be limited by the spatial excitation profile, which for sharply focused beams can approach ~1 ps time scales.......We demonstrate time-resolved terahertz spectroscopy inside a novel parallel plate waveguide where one of the metallic plates is replaced by a transparent conducting oxide. Considerable improvements to the waveguide loss coefficient are shown, with a power absorption coefficient of 4cm-1 at 0.5 THz...

  15. Time-resolved laser-induced breakdown spectroscopy of aluminum

    Institute of Scientific and Technical Information of China (English)

    LIU Xian-yun; ZHANG Wei-jun; WANG Zhen-ya; HAO Li-qing; HUANG Ming-qiang; ZHAO Wen-wu; LONG Bo; Zhao Wei

    2008-01-01

    We develop a system to measure the elemental composition of unprepared samples using laser-induced breakdown spectroscopy (LIBS) in our laboratory, which can be used for the determination of elements in solids, liquids and aerosols. A description of the instrumentation, including laser, sample chamber and detection, is followed by a brief discussion. The time-resolved LIBS of aluminum at atmospheric pressure is presented. At the end, the possibilities and later uses of this technique are briefly discussed.

  16. Time-Resolved Infrared Spectroscopy in Supercritical Fluids

    OpenAIRE

    George, Michael W.; Poliakoff, Martyn; Sun, Xue-Zhong; Grills, David C.

    1999-01-01

    We have used fast Time-resolved Infrared Spectroscopy (TRIR) to probe organometallic reactions in supercritical fluids on the nanosecond time-scale. This has allowed us to identify, for the first time in solution at room temperature, organometallic noble gas complexes which are formed following irradiation of metal carbonyls in supercritical noble gas solution. We have found that these complexes are surprisingly stable and have comparable reactivity to organometallic alkane complexes. We have...

  17. Probing Local Environments by Time-Resolved Stimulated Emission Spectroscopy

    OpenAIRE

    Ana Rei; Graham Hungerford; Michael Belsley; Ferreira, M. Isabel C.; Peter Schellenberg

    2012-01-01

    Time-resolved stimulated emission spectroscopy was employed to probe the local environment of DASPMI (4-(4-(dimethylamino)styryl)-N-methyl-pyridinium iodide) in binary solvents of different viscosity and in a sol-gel matrix. DASPMI is one of the molecules of choice to probe local environments, and the dependence of its fluorescence emission decay on viscosity has been previously used for this purpose in biological samples, solid matrices as well as in solution. The results presented in this p...

  18. Probing Local Environments by Time-Resolved Stimulated Emission Spectroscopy

    Directory of Open Access Journals (Sweden)

    Ana Rei

    2012-01-01

    Full Text Available Time-resolved stimulated emission spectroscopy was employed to probe the local environment of DASPMI (4-(4-(dimethylaminostyryl-N-methyl-pyridinium iodide in binary solvents of different viscosity and in a sol-gel matrix. DASPMI is one of the molecules of choice to probe local environments, and the dependence of its fluorescence emission decay on viscosity has been previously used for this purpose in biological samples, solid matrices as well as in solution. The results presented in this paper show that time-resolved stimulated emission of DASPMI is a suitable means to probe the viscosity of local environments. Having the advantage of a higher time resolution, stimulated emission can provide information that is complementary to that obtained from fluorescence decay measurements, making it feasible to probe systems with lower viscosity.

  19. Time-resolved terahertz spectroscopy of semiconductor nanostructures

    DEFF Research Database (Denmark)

    Porte, Henrik

    This thesis describes time-resolved terahertz spectroscopy measurements on various semiconductor nanostructures. The aim is to study the carrier dynamics in these nanostructures on a picosecond timescale. In a typical experiment carriers are excited with a visible or near-infrared pulse and by...... measuring the transmission of a terahertz probe pulse, the photoconductivity of the excited sample can be obtained. By changing the relative arrival time at the sample between the pump and the probe pulse, the photoconductivity dynamics can be studied on a picosecond timescale. The rst studied semiconductor...

  20. Time-resolved photoluminescence spectroscopy of organic-plasmonic hybrids

    DEFF Research Database (Denmark)

    Leißner, Till; Brewer, Jonathan R.; Fiutowski, Jacek;

    We study the optical properties of organic thin films and crystalline organic nanofibers as well as their interaction with plasmonic materials by means of laser-scanning fluorescence lifetime imaging microscopy (FLIM) and time-resolved photoluminescence spectroscopy (TR-PLS). The aim of our......-carrier dynamics in such systems. In this contribution we will show how the interaction of organic nanofibers placed on top of regular arrays of nanostructures leads to a significantly enhanced second-harmonic response and, at the same time, an increased decay rate of the photoluminescence lifetime....

  1. Mobile Charge Generation Dynamics in P3HT:PCBM Observed by Time-Resolved Terahertz Spectroscopy

    DEFF Research Database (Denmark)

    Cooke, D. G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2012-01-01

    Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale.......Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale....

  2. Time resolved optical emission spectroscopy of an HPPMS coating process

    International Nuclear Information System (INIS)

    This paper deals with the time resolved optical emission spectroscopy of a high power pulse magnetron sputtering (HPPMS) physical vapour deposition coating process. With an industrial coating unit CC800/9 HPPMS (CemeCon AG, Wuerselen) a (Cr,Al,Si)N coating was deposited. During the coating process, an absolute calibrated Echelle spectrometer (ESA-3000) measured the intensities of the spectral lines of chromium (Cr), aluminium (Al) and molecular bands of nitrogen (N2). Time resolved measurements enable us to calculate different parameters such as the average velocity of sputtered Al and Cr atoms or the internal plasma parameters electron density ne and electron temperature kTe with a time resolution of 20 μs. With these parameters, we determine the ionization rates of Al, Cr, Ar and Kr atoms and the deposition densities of Al and Cr atoms. Thus simulated deposition densities of 1.75 x 1020 m-2 s-1 for chromium and 1.7 x 1022 m-2 s-1 for aluminium are reached.

  3. Diagnosis of meningioma by time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Butte, Pramod V; Pikul, Brian K; Hever, Aviv; Yong, William H; Black, Keith L; Marcu, Laura

    2005-01-01

    We investigate the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as an adjunctive tool for the intraoperative rapid evaluation of tumor specimens and delineation of tumor from surrounding normal tissue. Tissue autofluorescence is induced with a pulsed nitrogen laser (337 nm, 1.2 ns) and the intensity decay profiles are recorded in the 370 to 500 nm spectral range with a fast digitizer (0.2 ns resolution). Experiments are conducted on excised specimens (meningioma, dura mater, cerebral cortex) from 26 patients (97 sites). Spectral intensities and time-dependent parameters derived from the time-resolved spectra of each site are used for tissue characterization. A linear discriminant analysis algorithm is used for tissue classification. Our results reveal that meningioma is characterized by unique fluorescence characteristics that enable discrimination of tumor from normal tissue with high sensitivity (>89%) and specificity (100%). The accuracy of classification is found to increase (92.8% cases in the training set and 91.8% in the cross-validated set correctly classified) when parameters from both the spectral and the time domain are used for discrimination. Our findings establish the feasibility of using TR-LIFS as a tool for the identification of meningiomas and enables further development of real-time diagnostic tools for analyzing surgical tissue specimens of meningioma or other brain tumors. PMID:16409091

  4. Time-resolved vibrational spectroscopy of a molecular shuttle.

    Science.gov (United States)

    Panman, Matthijs R; Bodis, Pavol; Shaw, Danny J; Bakker, Bert H; Newton, Arthur C; Kay, Euan R; Leigh, David A; Buma, Wybren Jan; Brouwer, Albert M; Woutersen, Sander

    2012-02-14

    Time-resolved vibrational spectroscopy is used to investigate the inter-component motion of an ultraviolet-triggered two-station molecular shuttle. The operation cycle of this molecular shuttle involves several intermediate species, which are observable in the amide I and amide II regions of the mid-IR spectrum. Using ab initio calculations on specific parts of the rotaxane, and by comparing the transient spectra of the normal rotaxane with that of the N-deuterated version, we can assign the observed vibrational modes of each species occurring during the shuttling cycle in an unambiguous way. The complete time- and frequency-dependent data set is analyzed using singular value decomposition (SVD). Using a kinetic model to describe the time-dependent concentrations of the transient species, we derive the absorption spectra associated with each stage in the operation cycle of the molecular shuttle, including the recombination of the charged species. PMID:22033540

  5. A Clinical Tissue Oximeter Using NIR Time-Resolved Spectroscopy.

    Science.gov (United States)

    Fujisaka, Shin-ichi; Ozaki, Takeo; Suzuki, Tsuyoshi; Kamada, Tsuyoshi; Kitazawa, Ken; Nishizawa, Mitsunori; Takahashi, Akira; Suzuki, Susumu

    2016-01-01

    The tNIRS-1, a new clinical tissue oximeter using NIR time-resolved spectroscopy (TRS), has been developed. The tNIRS-1 measures oxygenated, deoxygenated and total hemoglobin and oxygen saturation in living tissues. Two-channel TRS measurements are obtained using pulsed laser diodes (LD) at three wavelengths, multi-pixel photon counters (MPPC) for light detection, and time-to-digital converters (TDC) for time-of-flight photon measurements. Incorporating advanced semiconductor devices helped to make the design of this small-size, low-cost and low-power TRS instrument possible. In order to evaluate the correctness and reproducibility of measurement data obtained with the tNIRS-1, a study using blood phantoms and healthy volunteers was conducted to compare data obtained from a conventional SRS device and data from an earlier TRS system designed for research purposes. The results of the study confirmed the correctness and reproducibility of measurement data obtained with the tNIRS-1. Clinical evaluations conducted in several hospitals demonstrated a high level of usability in clinical situations and confirmed the efficacy of measurement data obtained with the tNIRS-1. PMID:26782242

  6. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    Science.gov (United States)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  7. Time-resolved spectroscopy of low-dimensional semiconductor structures

    Science.gov (United States)

    Murphy, Joseph R.

    This dissertation is a survey of ultrafast time-resolved optical measurements conducted on a variety of low-dimensional semiconductor systems to further the understanding of the dynamic behavior in the following systems: ZnMnTe/ZnSe quantum dots, ZnTe/ZnMnSe quantum dots, InGaAs quantum wells, CdMnSe colloidal quantum dots, multi-shell CdSe/CdMnS/CdS colloidal nanoplatelets, and graphene and graphene-related solutions and films. Using time-resolved photoluminescence to study epitaxially-grown ZnTe and ZnMnTe quantum dots in corresponding ZnMnSe and ZnSe matrices, the location dependence of manganese ions in respect to magnetic polaron formation is shown. The structure with manganese ions located in the matrix exhibited magnetic polaron behavior consistent with previous literature, whereas the structure with the magnetic ions located within the quantum dots exhibited unconventional magnetic polaron properties. These properties, including temperature and magnetic field insensitivity, were explained through the use of a model that predicted an increased internal magnetic field due to a decreased effective volume of the magnetic polaron and a higher effective temperature due to laser heating. Magneto-time-resolved photoluminescence measurements on a system of colloidal CdMnSe quantum dots show that the magnetic polaron properties differ significantly from the epitaxially grown quantum dots. First the timescales at which the magnetic polaron forms and the polarization saturates are different by more than an order of magnitude, and second, the magnetic polaron energy exhibited step-like behavior as the strength of the externally applied magnetic field is increased. The field dependent MP formation energy that is observed experimentally is explained as due to the breaking of the antiferromagnetic coupling of Mn dimers within the QDs. This model is further verified by the observation of quantized behavior in the Zeeman energy splitting. Through the use of magneto

  8. [Laser-time-resolved fluorescence spectroscopy in immunoassays].

    Science.gov (United States)

    Pan, L; Du, J; Xie, W; Du, Q; Yun, Q

    2000-06-01

    This paper described a laser-excited time-resolved fluoroimmunoassay set. It made lanthanide ion to couple the anhydrde of diethylenetriaminepentaacetic acid (DTPAA) for labeling antibodies. The experiment used polystyrene tap coated with HCV antigen as the solid phase and a chelate of the rare earth metal europium as fluorescent label. A nitrogen laser beam was used to excite the Eu3- chelates and after 60 microseconds delay time, the emission fluorescence was measured. Background fluorescence of short lifetimes caused by serum components and Raman scattering can be eliminated by set the delay time. In the system condition, fluorescent spectra and fluorescent lifetimes of Eu3+ beta-naphthoyltrifluroacetone (NTA) chelates were measured. The fluorescent lifetime value is 650 microseconds. The maximum emission wavelength is 613 nm. The linear range of europium ion concentration is 1 x 10(-7)-1 x 10(-11) g.mL-1 and the detection limit is 1 x 10(-13) g.mL-1. The relative standard deviation of determination (n = 12) for samples at 0.01 ng.mL-1 magnitude is 6.4%. Laser-TRFIA was also found to be suitable for diagnosis of HCV. The sensitivity and specificity were comparable to enzyme immunoassay. The result was obtained with laser-TRFIA for 29 human correlated well with enzyme immunoassay. PMID:12958930

  9. Application of microfluidic devices for time resolved FTIR spectroscopy

    International Nuclear Information System (INIS)

    Within this thesis, micro fluidic mixers, operated in continuous flow mode, were used for time resolved FTIR studies of chemical reactions in aqueous solution. Any chemical reaction, that can be started upon mixing two reagents, can be examined with this technique. The mixing channel also serves as the observation window for the IR measurements. The actual measurements take place at well defined spots along this channel, corresponding to specific reaction times: moving the measurement spot (100 × 100 μm2) towards the entry yields shorter reaction times, moving it towards the channel's end gives longer reaction times. The temporal resolution of the experiment depends on the flow rate inside the mixing channel and the spacing between subsequent measurement points. Fast flow rates, limited by the back pressure of the mixer leading to leakages, allow time resolutions in the sub-millisecond time range using a standard FTIR microscope, whereas slow flow rates allow the measurement of reaction times up to 1000 ms. Evaluating the mixer using a fast chemical reaction resulted in mixing times of approximately 5 ms and a homogeneous distribution of the liquids across the width of the mixing channel. The mixer was then used for the measurement of the H/D exchange on carbohydrates, the complex formaldehyde sulfite clock reaction, and the folding of the protein ubiquitin from its native to the ''A'' state, induced by mixing it with an acidified methanol solution. For cleaning the mixer a software tool, called ATLAS, was developed in LabVIEW, which was used to automatize the necessary cleaning steps performed by a dedicated flow system. Additionally, the micro mixer technology was combined with the step scan measurement technique using a beam condenser focusing the IR beam of an FTIR spectrometer down to a spot size of 1 mm diameter and through the mixer. The laser light, initiating the chemical reaction inside the mixing channel, was coupled into the focusing unit using a

  10. Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Vlček Jr., Antonín; Kvapilová, Hana; Towrie, M.; Záliš, Stanislav

    2015-01-01

    Roč. 48, č. 3 (2015), s. 868-876. ISSN 0001-4842 Institutional support: RVO:61388955 Keywords : electron transfer * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 22.323, year: 2014

  11. A high accuracy broadband measurement system for time resolved complex bioimpedance measurements

    International Nuclear Information System (INIS)

    Bioimpedance measurements are useful tools in biomedical engineering and life science. Bioimpedance is the electrical impedance of living tissue and can be used in the analysis of various physiological parameters. Bioimpedance is commonly measured by injecting a small well known alternating current via surface electrodes into an object under test and measuring the resultant surface voltages. It is non-invasive, painless and has no known hazards. This work presents a field programmable gate array based high accuracy broadband bioimpedance measurement system for time resolved bioimpedance measurements. The system is able to measure magnitude and phase of complex impedances under test in a frequency range of about 10–500 kHz with excitation currents from 10 µA to 5 mA. The overall measurement uncertainties stay below 1% for the impedance magnitude and below 0.5° for the phase in most measurement ranges. Furthermore, the described system has a sample rate of up to 3840 impedance spectra per second. The performance of the bioimpedance measurement system is demonstrated with a resistor based system calibration and with measurements on biological samples. (paper)

  12. Time-resolved photoelectron spectroscopy and ab initio multiple spawning studies of hexamethylcyclopentadiene

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.;

    2014-01-01

    Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....

  13. XPS for time resolved X-ray spectroscopy of plasmas

    International Nuclear Information System (INIS)

    Photoelectron spectroscopy is based on the simple energy conservation relation between a photon and an electron, hν = E /sub b/ + E /sub k/ , where hν is the photon energy, E /sub k/ is the electron kinetic energy and E /sub b/ is the binding energy of the electron ejected by the photon. In photoelectron spectroscopy, monochromatic photons are used to extract information about the various E /sub b/ 's in an atomic system by measuring E /sub k/ . By using atomic systems having a single electronic level with significant photoionization cross-section at the photon energies of interest it is also possible to find the energy of photons in a polychromatic source, again by measuring E /sub k/

  14. TIME-RESOLVED INFRARED SPECTROSCOPY IN THE U121R BEAMLINE AT THE NSLS

    International Nuclear Information System (INIS)

    A facility for performing time-resolved infrared spectroscopy has been developed at the NSLS, primarily at beamline U12IR. The pulsed IR light from the synchrotron is used to perform pump-probe spectroscopy. The authors present here a description of the facility and results for the relaxation of photoexcitations in both a semiconductor and superconductor

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

    International Nuclear Information System (INIS)

    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

  16. Applications of time-resolved terahertz spectroscopy in ultrafast carrier dynamics

    Institute of Scientific and Technical Information of China (English)

    Qingli Zhou; Xicheng Zhang

    2011-01-01

    1.Introduction Terahertz time-domain spectroscopy (THz-TDS)[1-3]is a powerful and coherent free-space technique in which nearly single-cycle electromagnetic pulse is generated and detected using femtosecond optical pulses.THz-TDS has been utilized as one of the important methods for material characterization in the past two decades.Because transmission or reflection of THz waves is sensitive to carrier density and mobility,an ultrafast THz-TDS system is required to provide time-resolved capability of material characterization in the THz region[4-6].In the past decade,one of the widely used time-resolved THz spectroscopy methods is optical-pump/THz probe (O/T)spectroscopy[3].%Three time-resolved terahertz (THz) spectroscopy methods (optical-pump/THz-probe spectroscopy, THz-pump/THz-probe spectroscopy, and THz-pump/optical-probe spectroscopy) are reviewed. These are used to characterize ultrafast dynamics in photo- or THz-excited semiconductors, superconductors, nanomateri-als, and other materials. In particular, the optical-pump/THz-probe spectroscopy is utilized to investigate carrier dynamics and the related intervalley scattering phenomena in semiconductors. The recent development of intense pulsed THz sources is expected to affect the research in nonlinear THz responses of various materials.

  17. Speciation of actinides in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

    International Nuclear Information System (INIS)

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) as a sensitive and selective method has been applied to the speciation of actinides in aqueous solution. Studies on hydrolysis and carbonate complexation of U(VI) and on determination of hydration number of Cm(III) are reported. (author)

  18. Time-resolved optical spectroscopy of the chest: is it possible to probe the lung?

    Science.gov (United States)

    Quarto, G.; Farina, A.; Pifferi, A.; Taroni, P.; Miniati, M.

    2013-06-01

    Monte Carlo simulations and preliminary time-resolved spectroscopy measurements were performed to investigate the feasibility of the in vivo optical diagnostics of lung conditions and diseases. Absorption and reduced scattering properties of the chest, arising from in vivo spectral measurements on volunteers are presented.

  19. Finite-difference time-domain analysis of time-resolved terahertz spectroscopy experiments

    DEFF Research Database (Denmark)

    Larsen, Casper; Cooke, David G.; Jepsen, Peter Uhd

    2011-01-01

    In this paper we report on the numerical analysis of a time-resolved terahertz (THz) spectroscopy experiment using a modified finite-difference time-domain method. Using this method, we show that ultrafast carrier dynamics can be extracted with a time resolution smaller than the duration of the THz...

  20. Time-resolved diffusing wave spectroscopy applied to dynamic heterogeneity imaging

    CERN Document Server

    Cheikh, M; Ettori, D; Tinet, E; Avrillier, S; Tualle, J M; Cheikh, Monia; Nghiem, Ha Lien; Ettori, Dominique; Tinet, Eric; Avrillier, Sigrid; Tualle, Jean-Michel

    2006-01-01

    We report in this paper what is to our knowledge the first observation of a time-resolved diffusing wave spectroscopy signal recorded by transillumination through a thick turbid medium: the DWS signal is measured for a fixed photon transit time, which opens the possibility of improving the spatial resolution. This technique could find biomedical applications, especially in mammography.

  1. Time-resolved terahertz spectroscopy of conjugated polymer/CdSe nanorod composites

    DEFF Research Database (Denmark)

    Cooke, David; Lek, Jun Y.; Krebs, Frederik C;

    2010-01-01

    report ultrafast carrier dynamics in hybrid CdSe nanorod / poly(3-hexythiophene) (P3HT) bulk heterojunction films measured by time-resolved terahertz spectroscopy, and compare to the well studied P3HT/phenyl-C61-butyric acid methyl ester (PCBM) blend. Both films show an improved peak...

  2. Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.;

    2014-01-01

    comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay of the...

  3. Broadband terahertz spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Wenhui Fan

    2011-01-01

    1.Introduction Spanning the frequency range between the infrared (IR) radiation and microwaves,terahertz (THz) waves are,also known as T-rays,T-lux,or simply called THz,assigned to cover the electromagnetic spectrum typically from 100 GHz (1011 Hz) to 10 THz (1013 Hz),namely,from 3 mm to 30 μm in wavelength,although slightly different definitions have been quoted by different authors.For a very long time,THz region is an almost unexplored field due to its rather unique location in the electromagnetic spectrum.Well-known techniques in optical or microwave region can not be directly employed in the THz range because optical wavelengths are too short and microwave wavelengths are too long compared to THz wavelengths.%An overview of the major techniques to generate and detect THz radiation so far, especially the major approaches to generate and detect coherent ultra-short THz pulses using ultra-short pulsed laser, has been presented. And also, this paper, in particularly, focuses on broadband THz spectroscopy and addresses on a number of issues relevant to generation and detection of broadband pulsed THz radiation as well as broadband time-domain THz spectroscopy (THz-TDS) with the help of ultra-short pulsed laser. The time-domain waveforms of coherent ultra-short THz pulses from photoconductive antenna excited by femtosecond laser with different pulse durations and their corresponding Fourier-transformed spectra have been obtained via the numerical simulation of ultrafast dynamics between femtosecond laser pulse and photoconductive material. The origins of fringes modulated on the top of broadband amplitude spectrum, which is measured by electric-optic detector based on thin nonlinear crystal and extracted by fast Fourier transformation, have been analyzed and the major solutions to get rid of these fringes are discussed.

  4. Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

    Institute of Scientific and Technical Information of China (English)

    Yin Jun; Yu Ling-Yao; Liu Xing; Wan Hui; Lin Zi-Yang; Niu Han-Ben

    2011-01-01

    In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of verious molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactious in the fields of biology, chemistry and naterial science.

  5. Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

    International Nuclear Information System (INIS)

    In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

  6. Time resolving imaging spectroscopy applied to the analysis of plasmas generated by pulsed lasers

    Energy Technology Data Exchange (ETDEWEB)

    Alvira, F C; Bilmes, G M [Centro de Investigaciones Opticas (CONICET La Plata-CIC) CC 3, 1897, Gonnet, La Plata, Buenos Aires (Argentina); Ponce, L; Arronte, M, E-mail: fcalvira@ciop.unlp.edu.ar [CICATA-IPN, Unidad Altamira, Altamira 89600, Tamps (Mexico)

    2011-01-01

    Time resolved imaging spectroscopy were used to study the spatial and temporal evolution of LIBS (Laser Induced Breakdown Spectroscopy) plasmas generated in Cu substrates by laser pulses of different duration. Long laser pulses (microsecond) and short laser pulses (nanosecond) as well as multipulse emission were used for excitation. Analysis was made by using an imaging spectrometer with time resolved detection. Results show that the use of long laser excitation pulses produce emission spectra with the same signal to noise ratio, but with lower resolution than those produced with shorter ones. The different species generated in LIBS experiments as neutral or single ionized have a different spatial distribution inside the plasma. We demonstrated that using spatial discrimination procedures is possible to obtain spectra with the same signal to noise ratio than those obtained with a gating detector. In this case an appreciable advantage in cost reduction is obtained by replacing the gating detector by a cheap screen.

  7. Time resolving imaging spectroscopy applied to the analysis of plasmas generated by pulsed lasers

    International Nuclear Information System (INIS)

    Time resolved imaging spectroscopy were used to study the spatial and temporal evolution of LIBS (Laser Induced Breakdown Spectroscopy) plasmas generated in Cu substrates by laser pulses of different duration. Long laser pulses (microsecond) and short laser pulses (nanosecond) as well as multipulse emission were used for excitation. Analysis was made by using an imaging spectrometer with time resolved detection. Results show that the use of long laser excitation pulses produce emission spectra with the same signal to noise ratio, but with lower resolution than those produced with shorter ones. The different species generated in LIBS experiments as neutral or single ionized have a different spatial distribution inside the plasma. We demonstrated that using spatial discrimination procedures is possible to obtain spectra with the same signal to noise ratio than those obtained with a gating detector. In this case an appreciable advantage in cost reduction is obtained by replacing the gating detector by a cheap screen.

  8. Following [FeFe] Hydrogenase Active Site Intermediates by Time-Resolved Mid-IR Spectroscopy.

    Science.gov (United States)

    Mirmohades, Mohammad; Adamska-Venkatesh, Agnieszka; Sommer, Constanze; Reijerse, Edward; Lomoth, Reiner; Lubitz, Wolfgang; Hammarström, Leif

    2016-08-18

    Time-resolved nanosecond mid-infrared spectroscopy is for the first time employed to study the [FeFe] hydrogenase from Chlamydomonas reinhardtii and to investigate relevant intermediates of the enzyme active site. An actinic 355 nm, 10 ns laser flash triggered photodissociation of a carbonyl group from the CO-inhibited state Hox-CO to form the state Hox, which is an intermediate of the catalytic proton reduction cycle. Time-resolved infrared spectroscopy allowed us to directly follow the subsequent rebinding of the carbonyl, re-forming Hox-CO, and determine the reaction half-life to be t1/2 ≈ 13 ± 5 ms at room temperature. This gives direct information on the dynamics of CO inhibition of the enzyme. PMID:27494400

  9. Simultaneous reference and differential waveform acquisition in time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Iwaszczuk, Krzysztof; Cooke, David; Fujiwara, Masazumi; Hashimoto, Hideki; Jepsen, Peter Uhd

    2009-01-01

    We present a new method for data acquisition in time-resolved terahertz spectroscopy experiments. Our approach is based on simultaneous collection of reference and differential THz scans. Both the optical THz generation beam and the pump beam are modulated at two different frequencies that are not...... harmonic with respect to each other. Our method allows not only twice as fast data acquisition but also minimization of noise connected to slowly varying laser power fluctuations and timing instabilities. Our use of the nonlinear crystal N-benzyl-2-methyl-4-nitroaniline (BNA) enables time-resolved THz...... spectroscopy to beyond 5 THz, thereby highlighting that the presented method is especially valuable at higher frequencies where phase errors in the data acquisition become increasingly important....

  10. Echelle-MEPSICRON time-resolved spectroscopy of the dwarf nova SS Cygni

    International Nuclear Information System (INIS)

    High-dispersion time-resolved spectroscopy of the dwarf nova SS Cygni was obtained during two consecutive days at the end of an outburst. The emission lines present a double-peaked profile with a peak-to-peak separation of 526±14 km s-1. The lines have a complex structure which includes a narrow asymmetric component coming from a hot spot in the accretion disc or from the chromosphere of the red dwarf. (author)

  11. Echelle-MEPSICRON time-resolved spectroscopy of the dwarf nova SS Cygni

    Energy Technology Data Exchange (ETDEWEB)

    Echevarria, J.; Tapia, M. (Universidad Nacional Autonoma de Mexico, Baja California (Mexico). Inst. de Astronomia); Diego, F. (Institute of Oceanographic Sciences, Godalming (UK)); Costero, R.; Ruiz, E.; Salas, L.; Gutierrez, L.; Enriquez, R. (Universidad Nacional Autonoma de Mexico, Mexico City (Mexico). Inst. de Astronomia)

    1989-10-15

    High-dispersion time-resolved spectroscopy of the dwarf nova SS Cygni was obtained during two consecutive days at the end of an outburst. The emission lines present a double-peaked profile with a peak-to-peak separation of 526{plus minus}14 km s{sup -1}. The lines have a complex structure which includes a narrow asymmetric component coming from a hot spot in the accretion disc or from the chromosphere of the red dwarf. (author).

  12. Time-Resolved Photoluminescence Spectroscopy: A Novel Technique for Determination of Luminescence of Quantum Dots

    Institute of Scientific and Technical Information of China (English)

    ZHENG Zhu-Hong; SHEN De-Zhen

    2007-01-01

    @@ The time-resolved photoluminescence (PL) spectroscopy measured by the gradually increasing start delay time is utilized as a tool for the determination of the luminescence of quantum dots (QDs). The luminescence evolution of self-assembled CdSe QDs during the luminescence decay is fully revealed in terms of the experiment technique.The characteristic narrow luminescence lines of self-assembled CdSe QDs are obtained with increasing start delay time.

  13. Charge transport in nanostructured materials for solar energy conversion studied by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Kužel, Petr; Sundström, V.

    2010-01-01

    Roč. 215, 2-3 (2010), s. 123-139. ISSN 1010-6030 R&D Projects: GA ČR(CZ) GP202/09/P099; GA AV ČR(CZ) IAA100100902; GA MŠk LC512 Institutional research plan: CEZ:AV0Z10100520 Keywords : time-resolved terahertz spectroscopy * ultrafast dynamics * bulk heterojunction * semiconductor nanostructures * transport * mobility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.243, year: 2010

  14. Time-resolved tunable diode laser absorption spectroscopy of pulsed plasma

    Czech Academy of Sciences Publication Activity Database

    Adámek, Petr; Olejníček, Jiří; Čada, Martin; Kment, Š.; Hubička, Zdeněk

    2013-01-01

    Roč. 38, č. 14 (2013), s. 2428-2430. ISSN 0146-9592 R&D Projects: GA MŠk LH12045; GA ČR(CZ) GAP205/11/0386; GA MŠk LD12002; GA MŠk LH12043 Institutional support: RVO:68378271 Keywords : diode lasers * plasma diagnostics * absorption spectroscopy * time resolved Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.179, year: 2013

  15. A beamline for time-resolved extreme ultraviolet and soft x-ray spectroscopy

    OpenAIRE

    Grilj, Jakob; Sistrunk, Emily; Koch, Markus; Gühr, Markus

    2013-01-01

    High harmonic generation is a convenient way to obtain extreme ultraviolet light from table-top laser systems and the experimental tools to exploit this simple and powerful light source for time-resolved spectroscopy are being developed by several groups. For these applications, brightness and stability of the high harmonic generation is a key feature. This article focuses on practical aspects in the generation of extreme ultraviolet pulses with ultrafast commercial lasers, namely generation ...

  16. Time-resolved detection of temperature, concentration, and pressure in a shock tube by intracavity absorption spectroscopy

    Science.gov (United States)

    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.

  17. Photoemission with high-order harmonics: A tool for time-resolved core-level spectroscopy

    DEFF Research Database (Denmark)

    Christensen, Bjarke Holl; Raarup, Merete Krog; Balling, Peter

    2010-01-01

    A setup for femtosecond time-resolved photoelectron spectroscopy of solid surfaces is presented. The photon energies for core-level spectroscopy experiments are created by high-order harmonic generation from infrared 120-femtosecond laser pulses focused in a Ne gas jet. The present experimental r...... from the sample are collected by a large-solid-angle time-of-flight electron spectrometer based on a parabolic-grid reflector. Results from experiments probing the Bi 5d core-levels are presented, and the results of preliminary pump-probe experiments are described....

  18. A flexible experimental setup for femtosecond time-resolved broad-band ellipsometry and magneto-optics

    International Nuclear Information System (INIS)

    A versatile experimental setup for femtosecond time-resolved ellipsometry and magneto-optical Kerr effect measurements in the visible light range is described. The apparatus is based on the pump-probe technique and combines a broad-band probing beam with an intense near-infrared pump. According to Fresnel scattering matrix formalism, the analysis of the reflected beam at different polarization states of the incident probe light allows one to determine the diagonal and the off-diagonal elements of the dielectric tensor in the investigated sample. Moreover, the pump-probe method permits to study the dynamics of the dielectric response after a short and intense optical excitation. The performance of the experimental apparatus is tested on CrO2 single crystals as a benchmark

  19. A flexible experimental setup for femtosecond time-resolved broad-band ellipsometry and magneto-optics

    Energy Technology Data Exchange (ETDEWEB)

    Boschini, F.; Hedayat, H.; Piovera, C.; Dallera, C. [Dipartimento di Fisica, Politecnico di Milano, p.zza Leonardo da Vinci 32, 20133 Milano (Italy); Gupta, A. [Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35487 (United States); Carpene, E., E-mail: ettore.carpene@polimi.it [CNR-IFN, Dipartimento di Fisica, Politecnico di Milano, p.zza Leonardo da Vinci 32, 20133 Milano (Italy)

    2015-01-15

    A versatile experimental setup for femtosecond time-resolved ellipsometry and magneto-optical Kerr effect measurements in the visible light range is described. The apparatus is based on the pump-probe technique and combines a broad-band probing beam with an intense near-infrared pump. According to Fresnel scattering matrix formalism, the analysis of the reflected beam at different polarization states of the incident probe light allows one to determine the diagonal and the off-diagonal elements of the dielectric tensor in the investigated sample. Moreover, the pump-probe method permits to study the dynamics of the dielectric response after a short and intense optical excitation. The performance of the experimental apparatus is tested on CrO{sub 2} single crystals as a benchmark.

  20. Broadband Rotational Spectroscopy

    Science.gov (United States)

    Pate, Brooks

    2014-06-01

    The past decade has seen several major technology advances in electronics operating at microwave frequencies making it possible to develop a new generation of spectrometers for molecular rotational spectroscopy. High-speed digital electronics, both arbitrary waveform generators and digitizers, continue on a Moore's Law-like development cycle that started around 1993 with device bandwidth doubling about every 36 months. These enabling technologies were the key to designing chirped-pulse Fourier transform microwave (CP-FTMW) spectrometers which offer significant sensitivity enhancements for broadband spectrum acquisition in molecular rotational spectroscopy. A special feature of the chirped-pulse spectrometer design is that it is easily implemented at low frequency (below 8 GHz) where Balle-Flygare type spectrometers with Fabry-Perot cavity designs become technologically challenging due to the mirror size requirements. The capabilities of CP-FTMW spectrometers for studies of molecular structure will be illustrated by the collaborative research effort we have been a part of to determine the structures of water clusters - a project which has identified clusters up to the pentadecamer. A second technology trend that impacts molecular rotational spectroscopy is the development of high power, solid state sources in the mm-wave/THz regions. Results from the field of mm-wave chirped-pulse Fourier transform spectroscopy will be described with an emphasis on new problems in chemical dynamics and analytical chemistry that these methods can tackle. The third (and potentially most important) technological trend is the reduction of microwave components to chip level using monolithic microwave integrated circuits (MMIC) - a technology driven by an enormous mass market in communications. Some recent advances in rotational spectrometer designs that incorporate low-cost components will be highlighted. The challenge to the high-resolution spectroscopy community - as posed by Frank De

  1. Time-resolved spectroscopy of plasma resonances in highly excited silicon and germanium

    International Nuclear Information System (INIS)

    The dynamics of the electron-hole plasma in silicon and germanium samples irradiated by 20 ps. 532 nm laser pulses has been investigated in the near infrared by the time-resolved picosecond optical spectroscopy. The experimental reflectivities and transmission are compared with the predictions of the thermal model for degenerate carrier distributions through the Drude formalism. Above a certain fluence, a significant deviation between measured and calculated values indicates a strong increase of the recombination rate as soon as the plasma resonances become comparable with the band gaps. These new plasmon-aided recombination channels are particularly pronounced in germanium. 15 refs., 8 figs

  2. Absorption spectroscopy of powdered materials using time-resolved diffuse optical methods.

    Science.gov (United States)

    D'Andrea, Cosimo; Obraztsova, Ekaterina A; Farina, Andrea; Taroni, Paola; Lanzani, Guglielmo; Pifferi, Antonio

    2012-11-10

    In this paper a novel method, based on time-resolved diffuse optical spectroscopy, is proposed to measure the absorption of small amounts of nanostructured powder materials independent of scattering. Experimental validation, in the visible and near-infrared spectral range, has been carried out on India Inkparticles. The effectiveness of the technique to measure scattering-free absorption is demonstrated on carbon nanotubes. The comparison between the absorption spectra acquired by the proposed method and conventional measurements performed with a commercial spectrophotometer is discussed. PMID:23142900

  3. Hole emission from Ge/Si quantum dots studied by time-resolved capacitance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kapteyn, C.M.A.; Lion, M.; Heitz, R.; Bimberg, D. [Technische Univ. Berlin (Germany). Inst. fuer Festkoerperphysik; Miesner, C.; Asperger, T.; Brunner, K.; Abstreiter, G. [Technische Univ. Muenchen, Garching (Germany). Walter-Schottky-Inst. fuer Physikalische Grundlagen der Halbleiterelektronik

    2001-03-01

    Emission of holes from self-organized Ge quantum dots (QDs) embedded in Si Schottky diodes is studied by time-resolved capacitance spectroscopy (DLTS). The DLTS signal is rather broad and depends strongly on the filling and detection bias conditions. The observed dependence is interpreted in terms of carrier emission from many-hole states of the QDs. The activation energies obtained from the DLTS measurements are a function of the amount of stored charge and the position of the Fermi level in the QDs. (orig.)

  4. Time-resolved and doppler-reduced laser spectroscopy on atoms

    International Nuclear Information System (INIS)

    Radiative lifetimes have been studied in neutral boron, carbon, silicon and strontium, in singly ionized gadolinium and tantalum and in molecular carbon monoxide and C2. The time-resolved techniques were based either on pulsed lasers or pulse-modulated CW lasers. Several techniques have been utilized for the production of free atoms and ions such as evaporation into an atomic beam, sputtering in hollow cathodes and laser-produced plasmas. Hyperfine interactions in boron, copper and strontium have been examined using quantum beat spectroscopy, saturation spectroscopy and collimated atomic beam spectroscopy. Measurement techniques based on effusive hollow cathodes as well as laser produced plasmas in atomic physics have been developed. Investigations on laser produced plasmas using two colour beam deflection tomography for determination of electron densities have been performed. Finally, new possibilities for view-time-expansion in light-in-flight holography using mode-locked CW lasers have been demonstrated. (au)

  5. A versatile and reconfigurable setup for all-terahertz time-resolved pump-probe spectroscopy

    Science.gov (United States)

    Elezzabi, A. Y.; Maraghechi, P.

    2012-05-01

    A versatile optical setup for all-terahertz (THz) time resolved pump-probe spectroscopy was designed and tested. By utilizing a dual THz pulse generator emitter module, independent and synchronized THz radiation pump and probe pulses were produced, thus eliminating the need for THz beam splitters and the limitations associated with their implementation. The current THz setup allows for precise control of the electric fields splitting ratio between the THz radiation pump and probe pulses, as well as in-phase, out-of-phase, and polarization dependent pump-probe spectroscopy. Since the present THz pump-probe setup does not require specialized THz radiation optical components, such as phase shifters, polarization rotators, or wide bandwidth beam splitters, it can be easily implemented with minimal alterations to a conventional THz time domain spectroscopy system. The present setup is valuable for studying the time dynamics of THz coherent phenomena in solid-state, chemical, and biological systems.

  6. Time-resolved spectroscopy of solid-state materials using an x-ray laser (Thesis)

    International Nuclear Information System (INIS)

    X-ray laser is a characteristic extreme ultraviolet (EUV) source with short pulse duration of several pico-seconds, narrow spectral width, and high coherence. In particular, x-ray laser with the wavelength of around 13 nm is expected as a powerful tool of various research fields such as EUV lithography because the multilayer mirror with high reflectance is commercially prepared. However, spectroscopic studies of materials optically excited with x-ray laser are few while imaging and interference measurements are intensively studied. In this study, the beam divergence and spatial coherence of x-ray laser was improved and applied to the measurement of time resolved emission spectroscopy of a solid-state material. The beam divergence of the x-ray laser was improved by double target configuration using two gain media. The nickel-like silver x-ray laser at the wavelength of 13.9 nm was improved to be spatially fully coherent beam with the divergence of 0.20 mrad. The number of coherent photons of this beam was 108 per pulse. The narrow divergence allowed us the beam transported by use of a simple mirror system with a small diameter of 1 inch. As an application of the x-ray laser, the UV emission from the zinc oxide (ZnO) single crystal excited by the 13.9 nm x-ray laser was observed and evaluated for EUV scintillator. The time-resolved emission spectra were observed for 13.9 nm excitation and 351 nm excitation. In both the excitation conditions, a prominent fluorescence peak of the ZnO exciton transition was observed at around 380 nm. The time profile at the peak of the spectra could be expressed by a double exponential decay with time constants of 1 ns and 3 ns in the both cases. The lifetimes and intensity ratio of the two decay components in the both cases were almost similar in spite of the huge difference in the excitation photon energy. The response time is sufficiently short for characterizing EUV lithography light sources having several nanoseconds duration. It

  7. Broadband transmission EPR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Wilfred R Hagen

    Full Text Available EPR spectroscopy employs a resonator operating at a single microwave frequency and phase-sensitive detection using modulation of the magnetic field. The X-band spectrometer is the general standard with a frequency in the 9-10 GHz range. Most (biomolecular EPR spectra are determined by a combination of the frequency-dependent electronic Zeeman interaction and a number of frequency-independent interactions, notably, electron spin - nuclear spin interactions and electron spin - electron spin interactions, and unambiguous analysis requires data collection at different frequencies. Extant and long-standing practice is to use a different spectrometer for each frequency. We explore the alternative of replacing the narrow-band source plus single-mode resonator with a continuously tunable microwave source plus a non-resonant coaxial transmission cell in an unmodulated external field. Our source is an arbitrary wave digital signal generator producing an amplitude-modulated sinusoidal microwave in combination with a broadband amplifier for 0.8-2.7 GHz. Theory is developed for coaxial transmission with EPR detection as a function of cell dimensions and materials. We explore examples of a doublet system, a high-spin system, and an integer-spin system. Long, straigth, helical, and helico-toroidal cells are developed and tested with dilute aqueous solutions of spin label hydroxy-tempo. A detection limit of circa 5 µM HO-tempo in water at 800 MHz is obtained for the present setup, and possibilities for future improvement are discussed.

  8. Capturing interfacial photoelectrochemical dynamics with picosecond time-resolved X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Neppl, Stefan; Shavorskiy, Andrey; Zegkinoglou, Ioannis; Fraund, Matthew; Slaughter, Daniel S; Troy, Tyler; Ziemkiewicz, Michael P; Ahmed, Musahid; Gul, Sheraz; Rude, Bruce; Zhang, Jin Z; Tremsin, Anton S; Glans, Per-Anders; Liu, Yi-Sheng; Wu, Cheng Hao; Guo, Jinghua; Salmeron, Miquel; Bluhm, Hendrik; Gessner, Oliver

    2014-01-01

    Time-resolved core-level spectroscopy using laser pulses to initiate and short X-ray pulses to trace photoinduced processes has the unique potential to provide electronic state- and atomic site-specific insight into fundamental electron dynamics in complex systems. Time-domain studies using transient X-ray absorption and emission techniques have proven extremely valuable to investigate electronic and structural dynamics in isolated and solvated molecules. Here, we describe the implementation of a picosecond time-resolved X-ray photoelectron spectroscopy (TRXPS) technique at the Advanced Light Source (ALS) and its application to monitor photoinduced electron dynamics at the technologically pertinent interface formed by N3 dye molecules anchored to nanoporous ZnO. Indications for a dynamical chemical shift of the Ru3d photoemission line originating from the N3 metal centre are observed ∼30 ps after resonant HOMO-LUMO excitation with a visible laser pump pulse. The transient changes in the TRXPS spectra are accompanied by a characteristic surface photovoltage (SPV) response of the ZnO substrate on a pico- to nanosecond time scale. The interplay between the two phenomena is discussed in the context of possible electronic relaxation and recombination pathways that lead to the neutralisation of the transiently oxidised dye after ultrafast electron injection. A detailed account of the experimental technique is given including an analysis of the chemical modification of the nano-structured ZnO substrate during extended periods of solution-based dye sensitisation and its relevance for studies using surface-sensitive spectroscopy techniques. PMID:25415599

  9. Microcontroller based resonance tracking unit for time resolved continuous wave cavity-ringdown spectroscopy measurements

    Science.gov (United States)

    Votava, Ondrej; Mašát, Milan; Parker, Alexander E.; Jain, Chaithania; Fittschen, Christa

    2012-04-01

    We present in this work a new tracking servoloop electronics for continuous wave cavity-ringdown absorption spectroscopy (cw-CRDS) and its application to time resolved cw-CRDS measurements by coupling the system with a pulsed laser photolysis set-up. The tracking unit significantly increases the repetition rate of the CRDS events and thus improves effective time resolution (and/or the signal-to-noise ratio) in kinetics studies with cw-CRDS in given data acquisition time. The tracking servoloop uses novel strategy to track the cavity resonances that result in a fast relocking (few ms) after the loss of tracking due to an external disturbance. The microcontroller based design is highly flexible and thus advanced tracking strategies are easy to implement by the firmware modification without the need to modify the hardware. We believe that the performance of many existing cw-CRDS experiments, not only time-resolved, can be improved with such tracking unit without any additional modification to the experiment.

  10. Time-resolved photoelectric spectroscopy of photorefractive CdTe:V crystals

    Energy Technology Data Exchange (ETDEWEB)

    Gnatenko, Yu P [Institute of Physics of NASU, 46 Prospekt Nauky, 03028 Kyiv (Ukraine); Piryatinski, Yu P [Institute of Physics of NASU, 46 Prospekt Nauky, 03028 Kyiv (Ukraine); Bukivskij, P M [Institute of Physics of NASU, 46 Prospekt Nauky, 03028 Kyiv (Ukraine); Kolendryckyj, D D [Institute of Physics of NASU, 46 Prospekt Nauky, 03028 Kyiv (Ukraine); Shigiltchoff, O A [Institute of Physics of NASU, 46 Prospekt Nauky, 03028 Kyiv (Ukraine); Gamernyk, R V [Lviv National University, 8 Kyrylo and Mefodiy Street, 29005 Lviv (Ukraine)

    2006-10-25

    The time-resolved photoelectric spectroscopy technique was used for the characterization of semi-insulating CdTe:V crystals using a short light pulse with 9 ns duration from a nitrogen laser (337.1 nm). The stationary monochromatic illumination of crystals let us measure the time-resolved photocurrent caused by the detrapping of the electrons photogenerated by the pulse laser excitation. The dependence of the intensity of pulse photocurrent on the energy of additional monochromatic illumination in the photorefractive CdTe:V crystals with the delay time t{sub d} = 5 ns, which corresponds to its maximum value, was investigated. The spectral dependence of pulse photocurrent produced by the detrapping process of electrons in CdTe:V crystals was measured under different intensities of the applied electric field. It is shown that the additional illumination at h-bar{omega}

  11. Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

    International Nuclear Information System (INIS)

    Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample

  12. A versatile approach for ratiometric time-resolved read-out of colorimetric chemosensors using broadband phosphors as secondary emitters

    International Nuclear Information System (INIS)

    Graphical abstract: -- Highlights: •A robust referencing schema for colorimetric indicators is proposed. •Time-resolved ratiometric read-out is realized. •(Photo)chemically stable inorganic phosphors are used. •The new method enables simple and low cost read-out set-up. •Application of the schema for sensing pH or carbon dioxide is demonstrated. -- Abstract: A new approach for referencing of colorimetric chemosensors is described. The sensing materials rely on combination of absorption-based indicators and inorganic phosphors. Chromium(III)-activated yttrium aluminum borate and gadolinium aluminum borate were chosen to illustrate the new sensing scheme due to their spectral properties and high chemical and photochemical stability. The ratiometric luminescence read-out becomes possible due to the overlap of at least one form of the indicator with broadband emission (650–900 nm) or excitation (400–700 nm) of the phosphor. Long luminescence decay time of the phosphors (80–150 μs) allows for complete elimination of background fluorescence originating from the media, optical components or the indicator. The versatile scheme enables robust read-out of numerous colorimetric chemosensors and probes. Examples of sensing pH (using a BF2-chelated tetraarylazadipyrromethene dye as an indicator) and carbon dioxide (a triphenylmethane dye as an indicator) are provided. It is also demonstrated that temperature can be accessed via luminescence decay time of the phosphor to enable compensation of the sensors for temperature effects

  13. Label-Free Toxin Detection by Means of Time-Resolved Electrochemical Impedance Spectroscopy

    Directory of Open Access Journals (Sweden)

    Paul Takhistov

    2010-01-01

    Full Text Available The real-time detection of trace concentrations of biological toxins requires significant improvement of the detection methods from those reported in the literature. To develop a highly sensitive and selective detection device it is necessary to determine the optimal measuring conditions for the electrochemical sensor in three domains: time, frequency and polarization potential. In this work we utilized a time-resolved electrochemical impedance spectroscopy for the detection of trace concentrations of Staphylococcus enterotoxin B (SEB. An anti-SEB antibody has been attached to the nano-porous aluminum surface using 3-aminopropyltriethoxysilane/glutaraldehyde coupling system. This immobilization method allows fabrication of a highly reproducible and stable sensing device. Using developed immobilization procedure and optimized detection regime, it is possible to determine the presence of SEB at the levels as low as 10 pg/mL in 15 minutes.

  14. Time-resolved pump-probe X-ray absorption fine structure spectroscopy of Gaq3

    International Nuclear Information System (INIS)

    Gallium(tris-8-hydroxyquinoline) (Gaq3) belongs to a class of metal organic compounds, used as electron transport layer and emissive layer in organic light emitting diodes. Many research activities have concentrated on the optical and electronic properties, especially of the homologue molecule aluminum(tris-8-hydroxyquinoline) (Alq3). Knowledge of the first excited state S1 structure of these molecules could provide deeper insight into the processes involved into the operation of electronic devices, such as OLEDs and, hence, it could further improve their efficiency and optical properties. Until now the excited state structure could not be determined experimentally. Most of the information about this structure mainly arises from theoretical calculations. X-ray absorption fine structure (XAFS) spectroscopy is a well developed technique to determine both, the electronic and the geometric properties of a sample. The connection of ultrashort pulsed X-ray sources with a pulsed laser system offers the possibility to use XAFS as a tool for studying the transient changes of a sample induced by a laser pulse. In the framework of this thesis a new setup for time-resolved pump-probe X-ray absorption spectroscopy at PETRA III beamline P11 was developed for measuring samples in liquid form. In this setup the sample is pumped into its photo-excited state by a femtosecond laser pump pulse with 343 nm wavelength and after a certain time delay probed by an X-ray probe pulse. In this way the first excited singlet state S1 of Gaq3 dissolved in benzyl alcohol was analyzed. A structural model for the excited state structure of the Gaq3 molecule based on the several times reproduced results of the XAFS experiments is proposed. According to this model it was found that the Ga-NA bond length is elongated, while the Ga-OA bond length is shortened upon photoexcitation. The dynamics of the structural changes were not the focus of this thesis. Nevertheless the excited state lifetime of Gaq3

  15. Structure-activity relationships of heterogeneous catalysts from time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Knowing the composition and the evolution of the bulk structure of a heterogeneous catalyst under working conditions (in situ) is a pre-requisite for understanding structure-activity relationships. X-ray absorption spectroscopy can be employed to study a catalytically active material in situ. In addition to steady-state investigations, the technique permits experiments with a time-resolution in the sub-second range to elucidate the solid-state kinetics of the reactions involved. Combined with mass spectrometry, the evolution of the short-range order structure of a heterogeneous catalyst, the average valence of the constituent metals, and the phase composition can be obtained. Here we present results obtained from time-resolved studies on the reduction of MoO3 in propene and in propene and oxygen

  16. Time-Resolved Spectroscopy of Quantum Cascade Lasers operated in Pulsed Mode

    International Nuclear Information System (INIS)

    Full text: Time-resolved spectroscopy with pump-probe technique is a good instrument for analyzing physical processes and material properties in quantum cascade lasers. This method was used for the characterization of lasers in continuous wave. Whereas pulsed operated laser are subject to permanent changes in their working point and thus their optical properties. In our work we present an adapted version of this measurement technique capable to study pulsed operated lasers. By synchronizing pump current and sampling we can acquire the pump pulses in narrow time slots (∼20 ns) where we assume constant working conditions. This novel measurement technique gives us the possibility to gather more accurate data including gain, phase, refractive index and calculate the temperature behaviour of quantum cascade lasers. (author)

  17. Bayesian Comparison of Fit Parameters: An Application to Time-Resolved X-Ray Spectroscopy

    Science.gov (United States)

    Kashyap, V.

    Analysis of X-ray data of the stars AD Leo and Wolf 630, obtained with ROSAT provide important clues to the structure of the coronae on these low-mass, main-sequence stars. In particular, time-resolved X-ray spectroscopy of these stars allow us to derive estimates for the low- and high-temperature components of the plasma emission measures. Using Bayes' theorem, we show that the high-temperature components are correlated with the X-ray light-curves of the stars, while the low-temperature components are steady. Thus we are able to model the low-temperature emission as relatively compact, quiescent, static coronal loops, and the high-temperature emission as unstable flaring components.

  18. Time-resolved two-dimensional vibrational spectroscopy of a short α-helix in water

    Science.gov (United States)

    Woutersen, Sander; Hamm, Peter

    2001-10-01

    Nonlinear two-dimensional (2D) vibrational spectroscopy has been used to investigate the amide I band of an alanine-based 21-residue α-helical peptide in aqueous solution. Whereas the linear absorption spectrum consists of a single, broad amide I band, the 2D vibrational spectrum clearly reveals that this band is composed of two amide I transitions, which are assigned to the A and E1 modes. The A-E1 frequency splitting is found to be approximately 10 cm-1. We find that the amide I band is inhomogeneously broadened due to conformational disorder of the helix. The 2D line shapes can be well described using distributions of the dihedral angles (φ,ψ) around their average values with a width of 20°, confirming previous molecular-dynamics studies. Time-resolved 2D measurements show that the conformation fluctuates on a time scale of picoseconds.

  19. Time-resolved luminescence spectroscopy of structurally disordered K3WO3F3 crystals

    Science.gov (United States)

    Omelkov, S. I.; Spassky, D. A.; Pustovarov, V. A.; Kozlov, A. V.; Isaenko, L. I.

    2016-08-01

    Three emission centers of exciton-like origin, with distinct relaxation time, emission and excitation spectra were revealed in K3WO3F3 and described taking into account its structural disordering. Low-temperature monoclinic phase of K3WO3F3 features few anion sites with mixed oxygen/fluorine occupancy per [WO3F3] octahedron. Therefore, different kinds of distorted octahedra form, providing different luminescence centers. The time-resolved luminescence spectroscopy technique was applied to distinguish these centers. The simultaneous thermal quenching of them above ∼200 K was qualitatively explained involving dynamic structural disorder of the compound. The energy transfer mechanism between centers was found and tentatively described by the diffusion of excitons. Apart from intrinsic luminescence, the PL of defect-related centers was discovered and the role of shallow charge carrier traps in the low-temperature persistent luminescence was revealed.

  20. Time-resolved spectroscopy of spin-current emission from a magnetic insulator

    Science.gov (United States)

    Tateno, Yuma; Fukami, Masaya; Tashiro, Takaharu; Ando, Kazuya

    2016-05-01

    We demonstrate time-resolved spectroscopy of spin-current emission from a magnetic insulator using the inverse spin Hall effect (ISHE). We measured magnetic field dependence of the spin-current emission in the time domain and found that the spectral shape of the ISHE voltage changes with time. The change in the spectral shape is due to field and power dependent temporal oscillation of the spin pumping driven by parametric magnons. The observed oscillating spin-current emission driven by dipole-exchange magnons is well reproduced by a model calculation based on the S theory. In contrast, the spin-current emission driven by short-wavelength exchange magnons cannot be reproduced with this model, illustrating an important role of higher-order nonlinear effects in the spin-current emission.

  1. Frame-Transfer Gating Raman Spectroscopy for Time-Resolved Multiscalar Combustion Diagnostics

    Science.gov (United States)

    Nguyen, Quang-Viet; Fischer, David G.; Kojima, Jun

    2011-01-01

    Accurate experimental measurement of spatially and temporally resolved variations in chemical composition (species concentrations) and temperature in turbulent flames is vital for characterizing the complex phenomena occurring in most practical combustion systems. These diagnostic measurements are called multiscalar because they are capable of acquiring multiple scalar quantities simultaneously. Multiscalar diagnostics also play a critical role in the area of computational code validation. In order to improve the design of combustion devices, computational codes for modeling turbulent combustion are often used to speed up and optimize the development process. The experimental validation of these codes is a critical step in accepting their predictions for engine performance in the absence of cost-prohibitive testing. One of the most critical aspects of setting up a time-resolved stimulated Raman scattering (SRS) diagnostic system is the temporal optical gating scheme. A short optical gate is necessary in order for weak SRS signals to be detected with a good signal- to-noise ratio (SNR) in the presence of strong background optical emissions. This time-synchronized optical gating is a classical problem even to other spectroscopic techniques such as laser-induced fluorescence (LIF) or laser-induced breakdown spectroscopy (LIBS). Traditionally, experimenters have had basically two options for gating: (1) an electronic means of gating using an image intensifier before the charge-coupled-device (CCD), or (2) a mechanical optical shutter (a rotary chopper/mechanical shutter combination). A new diagnostic technology has been developed at the NASA Glenn Research Center that utilizes a frame-transfer CCD sensor, in conjunction with a pulsed laser and multiplex optical fiber collection, to realize time-resolved Raman spectroscopy of turbulent flames that is free from optical background noise (interference). The technology permits not only shorter temporal optical gating (down

  2. Design and evaluation of a device for fast multispectral time-resolved fluorescence spectroscopy and imaging

    International Nuclear Information System (INIS)

    The application of time-resolved fluorescence spectroscopy (TRFS) to in vivo tissue diagnosis requires a method for fast acquisition of fluorescence decay profiles in multiple spectral bands. This study focusses on development of a clinically compatible fiber-optic based multispectral TRFS (ms-TRFS) system together with validation of its accuracy and precision for fluorescence lifetime measurements. It also presents the expansion of this technique into an imaging spectroscopy method. A tandem array of dichroic beamsplitters and filters was used to record TRFS decay profiles at four distinct spectral bands where biological tissue typically presents fluorescence emission maxima, namely, 390, 452, 542, and 629 nm. Each emission channel was temporally separated by using transmission delays through 200 μm diameter multimode optical fibers of 1, 10, 19, and 28 m lengths. A Laguerre-expansion deconvolution algorithm was used to compensate for modal dispersion inherent to large diameter optical fibers and the finite bandwidth of detectors and digitizers. The system was found to be highly efficient and fast requiring a few nano-Joule of laser pulse energy and <1 ms per point measurement, respectively, for the detection of tissue autofluorescent components. Organic and biological chromophores with lifetimes that spanned a 0.8–7 ns range were used for system validation, and the measured lifetimes from the organic fluorophores deviated by less than 10% from values reported in the literature. Multi-spectral lifetime images of organic dye solutions contained in glass capillary tubes were recorded by raster scanning the single fiber probe in a 2D plane to validate the system as an imaging tool. The lifetime measurement variability was measured indicating that the system provides reproducible results with a standard deviation smaller than 50 ps. The ms-TRFS is a compact apparatus that makes possible the fast, accurate, and precise multispectral time-resolved fluorescence

  3. Studies of Minerals, Organic and Biogenic Materials through Time-Resolved Raman Spectroscopy

    Science.gov (United States)

    Garcia, Christopher S.; Abedin, M. Nurul; Ismail, Syed; Sharma, Shiv K.; Misra, Anupam K.; Nyugen, Trac; Elsayed-Ali, hani

    2009-01-01

    A compact remote Raman spectroscopy system was developed at NASA Langley Research center and was previously demonstrated for its ability to identify chemical composition of various rocks and minerals. In this study, the Raman sensor was utilized to perform time-resolved Raman studies of various samples such as minerals and rocks, Azalea leaves and a few fossil samples. The Raman sensor utilizes a pulsed 532 nm Nd:YAG laser as excitation source, a 4-inch telescope to collect the Raman-scattered signal from a sample several meters away, a spectrograph equipped with a holographic grating, and a gated intensified CCD (ICCD) camera system. Time resolved Raman measurements were carried out by varying the gate delay with fixed short gate width of the ICCD camera, allowing measurement of both Raman signals and fluorescence signals. Rocks and mineral samples were characterized including marble, which contain CaCO3. Analysis of the results reveals the short (approx.10-13 s) lifetime of the Raman process, and shows that Raman spectra of some mineral samples contain fluorescence emission due to organic impurities. Also analyzed were a green (pristine) and a yellow (decayed) sample of Gardenia leaves. It was observed that the fluorescence signals from the green and yellow leaf samples showed stronger signals compared to the Raman lines. Moreover, it was also observed that the fluorescence of the green leaf was more intense and had a shorter lifetime than that of the yellow leaf. For the fossil samples, Raman shifted lines could not be observed due the presence of very strong short-lived fluorescence.

  4. Time-resolved infrared spectroscopy of organic and biological transient species

    International Nuclear Information System (INIS)

    Chapter 1 - Introduction. A short introduction to TRIR spectroscopy is given, including a description of different experimental approaches to nanosecond TRIR. Previous applications of TRIR to the study of organic photochemistry and biological systems are outlined. The experimental methods used within this thesis are briefly described, particularly with reference being made to previous, more detailed accounts of the techniques. Chapter 2 - Photopolymerisation Initiators. A description of previous spectroscopic studies on the photochemistry of photopolymerisation initiators is given, focusing on phosphine oxides, and α-hydroxy and (α-amino ketones. A combination of time-resolved s2-FTIR, diode laser based TRIR and ultrafast TRIR have been used in order to provide insight into the photochemistry of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. The reactivity of its daughter 2,4,6-trimethylbenzoyl radical towards a range of radical quenchers (n-butyl acrylate, thiophenol, bromotrichloromethane and oxygen) has been determined. Other commercial photoinitiators have been investigated and the reactivities of their daughter benzoyl radicals have also been measured. Chapter 3 - Protein Folding. This chapter starts by outlining some of the unanswered questions concerning the folding of proteins. A description of different experimental approaches for obtaining structural and conformational information on proteins is given. The focus is then directed to methodologies and previous experiments that have been used for obtaining time-resolved information on conformational changes that occur when a protein folds or unfolds. A variable temperature steady-state FTIR study of a small β-hairpin model peptide has revealed that hydrogen bonding plays a rather insignificant role in the stabilisation of the β-hairpin. (author)

  5. Time-resolved X-ray spectroscopies of chemical systems: New perspectives.

    Science.gov (United States)

    Chergui, Majed

    2016-05-01

    The past 3-5 years have witnessed a dramatic increase in the number of time-resolved X-ray spectroscopic studies, mainly driven by novel technical and methodological developments. The latter include (i) the high repetition rate optical pump/X-ray probe studies, which have greatly boosted the signal-to-noise ratio for picosecond (ps) X-ray absorption spectroscopy studies, while enabling ps X-ray emission spectroscopy (XES) at synchrotrons; (ii) the X-ray free electron lasers (XFELs) are a game changer and have allowed the first femtosecond (fs) XES and resonant inelastic X-ray scattering experiments to be carried out; (iii) XFELs are also opening the road to the development of non-linear X-ray methods. In this perspective, I will mainly focus on the most recent technical developments and briefly address some examples of scientific questions that have been addressed thanks to them. I will look at the novel opportunities in the horizon. PMID:27376102

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-06-04

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

  7. Advancements in time-resolved x-ray laser induced time-of-flight photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; Widmann, K; Ao, T; Ping, Y; Hunter, J; Ng, A

    2005-07-28

    Time-resolved soft x-ray photoelectron spectroscopy is used to probe the non-steady-state evolution of the valence band electronic structure of laser heated ultra-thin (50 nm) metal foils and bulk semiconductors. Single-shot soft x-ray laser induced time-of-flight photoelectron spectroscopy with picosecond time resolution was used in combination with optical measurements of the disassembly dynamics that have shown the existence of a metastable liquid phase in fs-laser heated metal foils persisting 4-5 ps. This metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.3-2.5 mJ laser energy focused in a large 500 x 700 {micro}m{sup 2} spot to create heated conditions of 0.2-1.8 x 10{sup 12} W cm{sup -2} intensity. The unique LLNL COMET compact tabletop soft x-ray laser source provided the necessary high photon flux, highly monoenergetic, picosecond pulse duration, and coherence for observing the evolution of changes in the valence band electronic structure of laser heated metals and semiconductors with picosecond time resolution. This work demonstrates the continuing development of a powerful new technique for probing reaction dynamics and changes of local order on surfaces on their fundamental timescales including phenomena such as non-thermal melting, chemical bond formation, intermediate reaction steps, and the existence of transient reaction products.

  8. Time-resolved X-ray spectroscopies of chemical systems: New perspectives

    Directory of Open Access Journals (Sweden)

    Majed Chergui

    2016-05-01

    Full Text Available The past 3–5 years have witnessed a dramatic increase in the number of time-resolved X-ray spectroscopic studies, mainly driven by novel technical and methodological developments. The latter include (i the high repetition rate optical pump/X-ray probe studies, which have greatly boosted the signal-to-noise ratio for picosecond (ps X-ray absorption spectroscopy studies, while enabling ps X-ray emission spectroscopy (XES at synchrotrons; (ii the X-ray free electron lasers (XFELs are a game changer and have allowed the first femtosecond (fs XES and resonant inelastic X-ray scattering experiments to be carried out; (iii XFELs are also opening the road to the development of non-linear X-ray methods. In this perspective, I will mainly focus on the most recent technical developments and briefly address some examples of scientific questions that have been addressed thanks to them. I will look at the novel opportunities in the horizon.

  9. Standoff Time-Resolved Laser-Based Spectroscopy Tools for Sample Characterization and Biosignature Detection

    Science.gov (United States)

    Gasda, P. J.; Acosta-Maeda, T.; Lucey, P. G.; Misra, A. K.; Sharma, S. K.; Taylor, J.

    2014-12-01

    The NASA Mars2020 rover will be searching for signs of past habitability and past life on Mars. Additionally, the rover mission will prepare a cache of highly significant samples for a future sample return mission. NASA requires these samples to be well characterized; the instruments on the rover must be capable of fine-scale in situ mineralogical or elemental analysis with emphasis on biosignature detection or characterization. We have been developing multiple standoff laser-based instruments at the University of Hawaii, Manoa that are capable of fine-scale in situ chemical analysis and biosignatures detection. By employing a time-resolved spectroscopy, we can perform elemental analysis with Laser-Induced Breakdown Spectroscopy (LIBS), mineral and organic analysis with Raman spectroscopy, and biosignature detection with Laser-Induced Fluorescence (LIF). Each of these techniques share the same optics and detection equipment, allowing us to integrate them into a single, compact instrument. High time-resolution (~100 ns/pulse) is the key to this instrument; with it, the detector only records data when the signal is the brightest. Spectra can be taken during the day, LIBS can be measured without a plasma light background, and the Raman signal can be separated from the mineral fluorescence signal. Since bio-organics have very short fluorescence lifetimes, the new instrument can be used to unambiguously detect bio-organics. The prototype uses a low power (0.5 mJ/pulse) 532 nm laser with a detection limit of drill holes, or outcrops, and then allow the slower but more precise instruments on the rover to characterize the regions of interest. Either of these prototypes would be ideally suited for future NASA missions, including human exploration missions. The next iterations of the instruments will be designed specifically for future astronaut explorers.

  10. Lasing dynamics study by femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy

    Science.gov (United States)

    Wei, Dang; Qing, Liao; Peng-Cheng, Mao; Hong-Bing, Fu; Yu-Xiang, Weng

    2016-05-01

    Femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy (FNOPAS) is a versatile technique with advantages of high sensitivity, broad detection bandwidth, and intrinsic spectrum correction function. These advantages should benefit the study of coherent emission, such as measurement of lasing dynamics. In this letter, the FNOPAS was used to trace the lasing process in Rhodamine 6G (R6G) solution and organic semiconductor nano-wires. High-quality transient emission spectra and lasing dynamic traces were acquired, which demonstrates the applicability of FNOPAS in the study of lasing dynamics. Our work extends the application scope of the FNOPAS technique. Project supported by the National Natural Science Foundation of China (Grant Nos. 20925313 and 21503066), the Innovation Program of Chinese Academy of Sciences (Grant No. KJCX2-YW-W25), the Postdoctoral Project of Hebei University, China, and the Project of Science and Technology Bureau of Baoding City, China (Grant No. 15ZG029).

  11. Noninvasive detection of concealed explosives: depth profiling through opaque plastics by time-resolved Raman spectroscopy.

    Science.gov (United States)

    Petterson, Ingeborg E Iping; López-López, María; García-Ruiz, Carmen; Gooijer, Cees; Buijs, Joost B; Ariese, Freek

    2011-11-15

    The detection of explosives concealed behind opaque, diffusely scattering materials is a challenge that requires noninvasive analytical techniques for identification without having to manipulate the package. In this context, this study focuses on the application of time-resolved Raman spectroscopy (TRRS) with a picosecond pulsed laser and an intensified charge-coupled device (ICCD) detector for the noninvasive identification of explosive materials through several millimeters of opaque polymers or plastic packaging materials. By means of a short (250 ps) gate which can be delayed several hundred picoseconds after the laser pulse, the ICCD detector allows for the temporal discrimination between photons from the surface of a sample and those from deeper layers. TRRS was applied for the detection of the two main isomers of dinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene as well as for various other components of explosive mixtures, including akardite II, diphenylamine, and ethyl centralite. Spectra were obtained through different diffuse scattering white polymer materials: polytetrafluoroethylene (PTFE), polyoxymethylene (POM), and polyethylene (PE). Common packaging materials of various thicknesses were also selected, including polystyrene (PS) and polyvinyl chloride (PVC). With the demonstration of the ability to detect concealed, explosives-related compounds through an opaque first layer, this study may have important applications in the security and forensic fields. PMID:21967622

  12. Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

    Science.gov (United States)

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-01

    We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime. PMID:26691822

  13. Light adaptation of the unicellular red alga, Cyanidioschyzon merolae, probed by time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Ueno, Yoshifumi; Aikawa, Shimpei; Kondo, Akihiko; Akimoto, Seiji

    2015-08-01

    Photosynthetic organisms change the quantity and/or quality of their pigment-protein complexes and the interactions among these complexes in response to light conditions. In the present study, we analyzed light adaptation of the unicellular red alga Cyanidioschyzon merolae, whose pigment composition is similar to that of cyanobacteria because its phycobilisomes (PBS) lack phycoerythrin. C. merolae were grown under different light qualities, and their responses were measured by steady-state absorption, steady-state fluorescence, and picosecond time-resolved fluorescence spectroscopies. Cells were cultivated under four monochromatic light-emitting diodes (blue, green, yellow, and red), and changes in pigment composition and energy transfer were observed. Cells grown under blue and green light increased their relative phycocyanin levels compared with cells cultured under white light. Energy-transfer processes to photosystem I (PSI) were sensitive to yellow and red light. The contribution of direct energy transfer from PBS to PSI increased only under yellow light, while red light induced a reduction in energy transfer from photosystem II to PSI and an increase in energy transfer from light-harvesting chlorophyll protein complex I to PSI. Differences in pigment composition, growth, and energy transfer under different light qualities are discussed. PMID:25577254

  14. A study of hydrolysis reaction of curium(III) by time resolved laser fluorescence spectroscopy

    International Nuclear Information System (INIS)

    The hydrolysis reaction of Cm3+ has been investigated by time resolved laser fluorescence spectroscopy (TRLFS) in 0.1 M NaClO4 at 25deg C under argon atmosphere. The experiment is carried out in the pH range from 6 to 10 for Cm(III) concentrations from 1.21 x 10-7 mol/l down to 3 x10-9 mol/l, which are substantially lower than solubility limits of the curium hydroxide each given pH. The primary and secondary hydrolysis constants determined are: logβ11 = 6.67 ± 0.18 for CmOH2+ and logβ12 = 12.06 ± 0.28 for Cm(OH)2+. These values are found to be in good agreement with the corresponding hydrolysis constants of Am3+ determined previously in our laboratory by the solubility experiment. However, the present values are one or many orders of magnitude smaller than the data known for Cm(III) in the literature. (orig.)

  15. ''Live'' Prussian blue fading by time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Prussian blue (PB) is an artists' pigment that has been frequently used in many artworks but poses several problems of conservation because of its fading under light and anoxia treatment. PB fading is due to the reduction of iron(III) into iron(II) and depends a lot on the object investigated. Due to the complexity of the structure, the precise physico-chemical mechanisms behind the redox process remain obscure. In this paper, we present a procedure to investigate light- and anoxia-induced fading of PB-paper samples by means of time resolved X-ray absorption spectroscopy performed at the Fe K-edge. A system composed of a visible light source and a flux-controlled environmental cell allowed light, gas and humidity to be modified in situ. The synchrotron X-ray beam was evidenced to induce a reduction of PB and to play a major role in the kinetics. The analysis of the PB fading kinetics of a sample submitted to various gas and light environments showed that both synchrotron beam and anoxia were influencing PB reduction in a correlated way. In comparison, light was found to play a minor role. Finally, we have demonstrated that the type of paper substrate could influence significantly the kinetics of reduction. Several hypotheses to explain the correlation between PB reduction mechanism and substrate are presented. (orig.)

  16. Time resolved spectroscopy of SGR J1550-5418 bursts detected with Fermi/GBM

    CERN Document Server

    Younes, G; van der Horst, A J; Baring, M G; Granot, J; Watts, A L; Bhat, P N; Collazzi, A; Gehrels, N; Gorgone, N; Gogus, E; Gruber, D; Grunblatt, S; Huppenkothen, D; Kaneko, Y; von Kienlin, A; van der Klis, M; Lin, L; Mcenery, J; van Putten, T; Wijers, R A M J

    2014-01-01

    We report on time-resolved spectroscopy of the 63 brightest bursts of SGR J1550-5418, detected with Fermi/Gamma-ray Burst Monitor during its 2008-2009 intense bursting episode. We performed spectral analysis down to 4 ms time-scales, to characterize the spectral evolution of the bursts. Using a Comptonized model, we find that the peak energy, E_peak, anti-correlates with flux, while the low-energy photon index remains constant at -0.8 up to a flux limit F~10^-5 erg s-1 cm-2. Above this flux value the E_peak-flux correlation changes sign, and the index positively correlates with flux reaching 1 at the highest fluxes. Using a two black-body model, we find that the areas and fluxes of the two emitting regions correlate positively. Further, we study here for the first time, the evolution of the temperatures and areas as a function of flux. We find that the area-kT relation follows lines of constant luminosity at the lowest fluxes, R^2 \\propto kT^-4, with a break at higher fluxes ($F>10^-5.5 erg s-1 cm-2). The are...

  17. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase

    International Nuclear Information System (INIS)

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D2O for reasons of experimental and theoretical suitability. However this is not water. Pure water H2O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  18. Photophysical and photochemical properties of 4-thiouracil: time-resolved IR spectroscopy and DFT studies.

    Science.gov (United States)

    Zou, Xiaoran; Dai, Xiaojuan; Liu, Kunhui; Zhao, Hongmei; Song, Di; Su, Hongmei

    2014-06-01

    Intensified research interests are posed with the thionucleobase 4-thiouracil (4-TU), due to its important biological function as site-specific photoprobe to detect RNA structures and nucleic acid-nucleic acid contacts. By means of time-resolved IR spectroscopy and density functional theory (DFT) studies, we have examined the unique photophysical and photochemical properties of 4-TU. It is shown that 4-TU absorbs UVA light and results in the triplet formation with a high quantum yield (0.9). Under N2-saturated anaerobic conditions, the reactive triplet undergoes mainly cross-linking, leading to the (5-4)/(6-4) pyrimidine-pyrimidone product. In the presence of O2 under aerobic conditions, the triplet 4-TU acts as an energy donor to produce singlet oxygen (1)O2 by triplet-triplet energy transfer. The highly reactive oxygen species (1)O2 then reacts readily with 4-TU, leading to the products of uracil (U) with a yield of 0.2 and uracil-6-sulfonate (U(SO3)) that is fluorescent at ~390 nm. The product formation pathways and product distribution are well rationalized by the joint B3LYP/6-311+G(d,p) calculations. From dynamics and mechanistic point of views, these results enable a further understanding for 4-TU acting as reactive precursors for photochemical reactions relevant to (1)O2, which has profound implications for photo cross-linking, DNA photodamage, as well as photodynamic therapy studies. PMID:24820207

  19. Time-resolved fluorescence polarization spectroscopy of visible and near infrared dyes in picosecond dynamics

    Science.gov (United States)

    Pu, Yang; Alfano, Robert R.

    2015-03-01

    Near-infrared (NIR) dyes absorb and emit light within the range from 700 to 900 nm have several benefits in biological studies for one- and/or two-photon excitation for deeper penetration of tissues. These molecules undergo vibrational and rotational motion in the relaxation of the excited electronic states, Due to the less than ideal anisotropy behavior of NIR dyes stemming from the fluorophores elongated structures and short fluorescence lifetime in picosecond range, no significant efforts have been made to recognize the theory of these dyes in time-resolved polarization dynamics. In this study, the depolarization of the fluorescence due to emission from rotational deactivation in solution will be measured with the excitation of a linearly polarized femtosecond laser pulse and a streak camera. The theory, experiment and application of the ultrafast fluorescence polarization dynamics and anisotropy are illustrated with examples of two of the most important medical based dyes. One is NIR dye, namely Indocyanine Green (ICG) and is compared with Fluorescein which is in visible range with much longer lifetime. A set of first-order linear differential equations was developed to model fluorescence polarization dynamics of NIR dye in picosecond range. Using this model, the important parameters of ultrafast polarization spectroscopy were identified: risetime, initial time, fluorescence lifetime, and rotation times.

  20. Carrier Formation Dynamics of Organic Photovoltaics as Investigated by Time-Resolved Spectroscopy

    Directory of Open Access Journals (Sweden)

    Kouhei Yonezawa

    2012-01-01

    Full Text Available Bulk heterojunction (BHJ based on a donor (D polymer and an acceptor (A fullerene derivative is a promising organic photovoltaics (OPV. In order to improve the incident photon-to-current efficiency (IPCE of the BHJ solar cell, a comprehensive understanding of the ultrafast dynamics of excited species, such as singlet exciton (D*, interfacial charge-transfer (CT state, and carrier (D+, is indispensable. Here, we performed femtosecond time-resolved spectroscopy of two prototypical BHJ blend films: poly(3-hexylthiophene (P3HT/[6,6]-phenyl C61-butyric acid methyl ester (PCBM blend film and poly(9,9′-dioctylfluorene-co-bithiophene (F8T2/[6,6]-phenyl C71-butyric acid methyl ester (PC70BM blend film. We decomposed differential absorption spectra into fast, slow, and constant components via two-exponential fitting at respective probe photon energies. The decomposition procedure clearly distinguished photoinduced absorptions (PIAs due to D*, CT, and D+. Based on these assignments, we will compare the charge dynamics between the F8T2/PC70BM and P3HT/PCBM blend films.

  1. Time-resolved spectroscopy of mitochondria, cells and tissues under normal and pathological conditions.

    Science.gov (United States)

    Beauvoit, B; Chance, B

    1998-07-01

    In this study, the detailed dependence of light scattering on tissue architecture and intracellular composition has been investigated. Firstly, we simulated the reduced scattering coefficient (mu(s)') of the rat liver using the Mie theory, the Rayleigh-Debye-Gans approximation and electron microscopy data. Then, the reduced scattering coefficient of isolated rat liver mitochondria, isolated hepatocytes and various rat tissues (i.e. perfused liver, brain, muscle, tumors) was measured at 780 nm by using time-resolved spectroscopy and a sample-substitution protocol. The comparison of the isolated mitochondria data with the isolated hepatocyte and whole liver measurements suggests that the mitochondrial compartment is the primary factor for light propagation in hepatic tissue, thus strengthening the relevance of the preliminary theoretical study. Nevertheless, the possibility that other intracellular components, such as peroxisomes and lysosomes, interfere with light propagation in rat liver is discussed. Finally, we demonstrate that light scattering in normal rat tissues and tumors is roughly proportional to the mitochondrial content, according to estimates of the mitochondrial protein content of the tissues. PMID:9746339

  2. Excitonic transitions in silicon nanostructures probed by time-resolved photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dovrat, M.; Shalibo, Y.; Arad, N.; Popov, I. [Racah Institute of Physics, Harvey M. Krueger Family Center for Nanoscience and Nanotechnology, Hebrew University of Jerusalem (Israel); Lee, S.T. [Center for Super-Diamond and Advanced Films, Department of Physics and Materials Science, City University of Hong Kong, Hong Kong (China); Sa' ar, A.

    2009-07-15

    Time-resolved photoluminescence spectroscopy has been utilized to reveal excitonic transitions in silicon nanowires and silicon nanocrystals. While previous works on porous silicon and silicon nanocrystals have shown a two-level splitting, e.g., singlet-triplet states, our measurements reveal the fine structure of the excitons including three semi-bright states and a ground dark excitonic state. Surprisingly, for silicon nanowires we have found the slowest semi-dark exciton to fall above the faster semi-bright excitonic state as opposed to silicon nanocrystals. The results are analyzed in terms of spin and orbital selection rules showing that the interchange in the level's hierarchy corresponds to a swap between spin-forbidden and orbitally-allowed states. We assign this surprising phenomenon to the relationship between the exchange interaction and the direct Coulomb interaction, which is affected by the dimensionality of the exciton. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Directory of Open Access Journals (Sweden)

    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.

  4. Intraoperative delineation of primary brain tumors using time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Butte, Pramod V; Fang, Qiyin; Jo, Javier A; Yong, William H; Pikul, Brian K; Black, Keith L; Marcu, Laura

    2010-01-01

    The goal of this study is to determine the potential of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as an adjunctive tool for delineation of brain tumor from surrounding normal tissue in order to assist the neurosurgeon in near-complete tumor excision. A time-domain TR-LIFS prototype apparatus (gated photomultiplier detection, fast digitizer) was used for recording tissue autofluorescence in normal cortex (NC), normal white matter (NWM), and various grades of gliomas intraoperatively. Tissue fluorescence was induced with a pulsed nitrogen laser (337 nm, 700 ps), and the intensity decay profiles were recorded in the 360- to 550-nm spectral range (10-nm interval). Histopathological analysis (hematoxylin & eosin) of the biopsy samples taken from the site of TR-LIFS measurements was used for validation of spectroscopic results. Preliminary results on 17 patients demonstrate that normal cortex (N=16) and normal white matter (N=3) show two peaks of fluorescence emission at 390 nm (lifetime=1.8+/-0.3 ns) and 460 nm (lifetime=0.8+/-0.1 ns). The 390-nm emission peak is absent in low-grade glioma (N=5; lifetime=1.1 ns) and reduced in high-grade glioma (N=9; lifetime=1.7+/-0.4 ns). The emission characteristics at 460 nm in all tissues correlated with the nicotinamide adenine dinucleotide fluorescence (peak: 440 to 460 nm; lifetime: 0.8 to 1.0 ns). These findings demonstrate the potential of using TR-LIFS as a tool for enhanced delineation of brain tumors during surgery. In addition, this study evaluates similarities and differences between TR-LIFS signatures of brain tumors obtained in vivo and those previously reported in ex vivo brain tumor specimens. PMID:20459282

  5. Intraoperative delineation of primary brain tumors using time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Butte, Pramod V.; Fang, Qiyin; Jo, Javier A.; Yong, William H.; Pikul, Brian K.; Black, Keith L.; Marcu, Laura

    2010-03-01

    The goal of this study is to determine the potential of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as an adjunctive tool for delineation of brain tumor from surrounding normal tissue in order to assist the neurosurgeon in near-complete tumor excision. A time-domain TR-LIFS prototype apparatus (gated photomultiplier detection, fast digitizer) was used for recording tissue autofluorescence in normal cortex (NC), normal white matter (NWM), and various grades of gliomas intraoperatively. Tissue fluorescence was induced with a pulsed nitrogen laser (337 nm, 700 ps), and the intensity decay profiles were recorded in the 360- to 550-nm spectral range (10-nm interval). Histopathological analysis (hematoxylin & eosin) of the biopsy samples taken from the site of TR-LIFS measurements was used for validation of spectroscopic results. Preliminary results on 17 patients demonstrate that normal cortex (N=16) and normal white matter (N=3) show two peaks of fluorescence emission at 390 nm (lifetime=1.8+/-0.3 ns) and 460 nm (lifetime=0.8+/-0.1 ns). The 390-nm emission peak is absent in low-grade glioma (N=5; lifetime=1.1 ns) and reduced in high-grade glioma (N=9; lifetime=1.7+/-0.4 ns). The emission characteristics at 460 nm in all tissues correlated with the nicotinamide adenine dinucleotide fluorescence (peak: 440 to 460 nm lifetime: 0.8 to 1.0 ns). These findings demonstrate the potential of using TR-LIFS as a tool for enhanced delineation of brain tumors during surgery. In addition, this study evaluates similarities and differences between TR-LIFS signatures of brain tumors obtained in vivo and those previously reported in ex vivo brain tumor specimens.

  6. High Resolution Time-resolved UCLES Spectroscopy of AE Aqr: I. The Secondary Star Revealed

    Science.gov (United States)

    Echevarria, J.; Diego, F.; Mills, D.; Connon Smith, R.

    2006-06-01

    High-dispersion time-resolved spectroscopy of the cataclysmic variable AE Aqr has been obtained. The emission lines have a complex structure that make difficult to measure the motion of the white dwarf. The cross correlation for the absorption lines shows a clear asymmetric profile as expected from a heated side of the red star. The spectral type for the secondary star varies from K2 to K5; there are clear indications that the temperature varies as a function of star longitude. The radial velocity analysis yield Kab = 165.2 ± 0.6 Km s-1 for the cross-correlated secondary star. The rotational velocity of the red star has been measured as a function of orbital period. It shows ellipsoidal variations with a period half the orbital period. The rotational velocities vary within the range Vrot sin i = 105 ± 3 Km s-1 and Vrot sin i = 130 ± 3 Km s-1. The former can be used to constrain the white dwarf semi-amplitude value to yield Kem = 139 ± 4 Km s-1 consistent with derived values from published radial velocity measurements. From a variation in the absorption line strength of 30%, we constrain the inclination angle to i = 58° ± 3. The estimated masses of the binary are: Mw = 1.07 ± 0.07 M? and Mr = 0.90 ± 0.05 M?. If this is correct we should expect a spectral type of G5 if the secondary star is a main sequence star. We suggest that the discrepancy is explained if the star has a radius 40% greater than a main sequence star for a mass of 0.90 M?.

  7. Effects of maturity on chlorophyll-related absorption in nectarines, measured by non-destructive time-resolved reflectance spectroscopy

    NARCIS (Netherlands)

    Tijskens, L.M.M.; Eccher Zerbini, P.C.; Vanoli, M.; Jacob, S.; Grassi, M.; Cebeddu, R.; Spinelli, L.; Torricelli, A.

    2006-01-01

    The ripening of fruits like nectarines and peaches is characterised by the decrease in chlorophyll content or colour of the fruit flesh. However, measuring the colour of fruit flesh is usually not conducted, as there is a lack of suitable techniques. Time-Resolved Reflectance Spectroscopy (TRS) is a

  8. Monitoring the Birth of an Electronic Wavepacket in a Neutral Molecule with Attosecond Time-Resolved Photoelectron Spectroscopy

    CERN Document Server

    Perveaux, Aurelie; Gatti, Fabien; Halasz, Gabor; Vibok, Agnes; Lasorne, Benjamin

    2014-01-01

    Numerical simulations are presented to validate the possible use of cutting-edge attosecond time- resolved photoelectron spectroscopy to observe in real time the creation of an electronic wavepacket and subsequent electronic motion in a neutral molecule photoexcited by a UV pump pulse within a few femtoseconds.

  9. Time-resolved photoluminescence spectroscopy of semiconductors for optical applications beyond the visible spectral range

    Energy Technology Data Exchange (ETDEWEB)

    Chernikov, Alexey A.

    2011-07-01

    The work discussed in this thesis is focused on the experimental studies regarding these three steps: (1) investigation of the fundamental effects, (2) characterization of new material systems, and (3) optimization of the semiconductor devices. In all three cases, the experimental technique of choice is photoluminescence (PL) spectroscopy. The thesis is organized as follows. Chapter 2 gives a summary of the PL properties of semiconductors relevant for this work. The first section deals with the intrinsic processes in an ideal direct band gap material, starting with a brief summary of the theoretical background followed by the overview of a typical PL scenario. In the second part of the chapter, the role of the lattice-vibrations, the internal electric fields as well as the influence of the band-structure and the dielectric environment are discussed. Finally, extrinsic PL properties are presented in the third section, focusing on defects and disorder in real materials. In chapter 3, the experimental realization of the spectroscopic studies is discussed. The time-resolved photoluminescence (TRPL) setup is presented, focusing on the applied excitation source, non-linear frequency mixing, and the operation of the streak camera used for the detection. In addition, linear spectroscopy setup for continous-wave (CW) PL and absorption measurements is illustrated. Chapter 4 aims at the study of the interactions between electrons and lattice-vibrations in semiconductor crystals relevant for the proper description of carrier dynamics as well as the heat-transfer processes. The presented discussion covers the experimental studies of many-body effects in phonon-assisted emission of semiconductors due to the carriercarrier Coulomb-interaction. The corresponding theoretical background is discussed in detail in chapter 2. The investigations are focused on the two main questions regarding electron-hole plasma contributions to the phonon-assisted light-matter interaction as well as

  10. Proton uptake mechanism of bacteriorhodopsin as determined by time-resolved stroboscopic-FTIR-spectroscopy.

    Science.gov (United States)

    Souvignier, G; Gerwert, K

    1992-11-01

    Bacteriorhodopsin's proton uptake reaction mechanism in the M to BR reaction pathway was investigated by time-resolved FTIR spectroscopy under physiological conditions (293 K, pH 6.5, 1 M KCl). The time resolution of a conventional fast-scan FTIR spectrometer was improved from 10 ms to 100 mus, using the stroboscopic FTIR technique. Simultaneously, absorbance changes at 11 wavelengths in the visible between 410 and 680 nm were recorded. Global fit analysis with sums of exponentials of both the infrared and visible absorbance changes yields four apparent rate constants, k(7) = 0.3 ms, k(4) = 2.3 ms, k(3) = 6.9 ms, k(6) = 30 ms, for the M to BR reaction pathway. Although the rise of the N and O intermediates is dominated by the same apparent rate constant (k(4)), protein reactions can be attributed to either the N or the O intermediate by comparison of data sets taken at 273 and 293 K. Conceptionally, the Schiff base has to be oriented in its deprotonated state from the proton donor (asp 85) to the proton acceptor (asp 96) in the M(1) to M(2) transition. However, experimentally two different M intermediates are not resolved, and M(2) and N are merged. From the results the following conclusions are drawn: (a) the main structural change of the protein backbone, indicated by amide I, amide II difference bands, takes place in the M to N (conceptionally M(2)) transition. This reaction is proposed to be involved in the "reset switch" of the pump, (b) In the M to N (conceptionally M(2)) transition, most likely, asp-85's carbonyl frequency shifts from 1,762 to 1,753 cm(-1) and persists in O. Protonation of asp-85 explains the red-shift of the absorbance maximum in O. (c) The catalytic proton uptake binding site asp-96 is deprotonated in the M to N transition and is reprotonated in O. PMID:19431858

  11. Complex formation of Cm(III) with formate studied by time-resolved laser fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Highlights: • Cm(III) complexation with formate is investigated at T = 20–90 °C. • The impact of formate on Cm(III) speciation increases with increasing temperature. • The complexation reactions of Cm(III) with formate are endothermic/entropy-driven. - Abstract: Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K0n(T) values for the formation of [Cm(Form)n](3−n)+ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)n](3−n)+ (n = 1, 2) with Cl− are obtained. The log K01(T) (2.11 (20 °C)–2.49 (90 °C)) and log K02(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K0n(T) values are used to derive the standard reaction enthalpies and entropies (ΔrH0m, ΔrS0m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive ΔrH0m and ΔrS0m values are obtained. Thus, both complexation steps are endothermic and entropy-driven

  12. Real-time TDDFT simulations of time-resolved core-level spectroscopies in solid state systems

    Science.gov (United States)

    Pemmaraju, Sri Chaitanya Das; Prendergast, David; Theory of Nanostructured Materials Facility Team

    The advent of sub-femtosecond time-resolved core-level spectroscopies based on high harmonic generated XUV pulses has enabled the study of electron dyanamics on characteristic femtosecond time-scales. Unambiguous interpretation of these powerful yet complex spectroscopies however requires the development of theoretical algorithms capable of modeling light-matter interaction across a wide energy range spanning both valence and core orbitals. In this context we present a recent implementation of the velocity-gauge formalism of real-time TDDFT within a linear combination of atomic orbital (LCAO) framework, which facilitates efficient numerical treatment of localized semi-core orbitals. Dynamics and spectra obtained from LCAO based simulations are compared to those from a real-space grid implementation. Potential applications are also illustrated by applying the method towards interpreting recent atto-second time-resolved IR-pump XUV-probe spectroscopies investigating sub-cycle excitation dynamics in bulk silicon.

  13. Ultrafast time-resolved spectroscopy of the light-harvesting complex 2 (LH2) from the photosynthetic bacterium Thermochromatium tepidum

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, R. E.

    2011-10-08

    The light-harvesting complex 2 from the thermophilic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption and fluorescence, sub-nanosecond-time-resolved fluorescence and femtosecond time-resolved transient absorption spectroscopy. The measurements were performed at room temperature and at 10 K. The combination of both ultrafast and steady-state optical spectroscopy methods at ambient and cryogenic temperatures allowed the detailed study of carotenoid (Car)-to-bacteriochlorophyll (BChl) as well BChl-to-BChl excitation energy transfer in the complex. The studies show that the dominant Cars rhodopin (N = 11) and spirilloxanthin (N = 13) do not play a significant role as supportive energy donors for BChl a. This is related with their photophysical properties regulated by long π-electron conjugation. On the other hand, such properties favor some of the Cars, particularly spirilloxanthin (N = 13) to play the role of the direct quencher of the excited singlet state of BChl.

  14. New time-resolved micro-photoluminescence spectroscopy of natural and synthetic analogue minerals

    Science.gov (United States)

    Panczer, G.; Ollier, N.; Champagnon, B.; Gaft, M.

    2003-04-01

    Minerals as well as geomaterials often present light emissions under UV or visible excitations. This property called photoluminescence is due to low concentration impurities such as the rare earths, the transition elements and the lanthanides. The induced color is used for ore prospection but only spectroscopic analyses indicate the nature of the emitted centers. However natural samples contained numerous luminescent centers simultaneously and with regular steady-state measurements (such as in cathodoluminescence) all the emissions are often over lapping. In order to record the contributions of each separate center, it is possible to use time-resolved measurements based on the decay time of the emissions and using pulsed laser excitation. Some characteristic examples will be presented on apatites, zircons as well as gemstones. Geomaterials present as well micro scale heterogeneities (growth zoning, inclusions, devitrification, microphases...). Precise identification and optical effects of such heterogeneities have to be taken into account. To reach the microscale using photo luminescence studies, a microscope has be modified to allowed pulsed laser injection (from UV to visible), beam focus with micro scale resolution on the sample (<10 μm), as well as time resolved collection of micro fluorescence. Such equipment allows now undertaking time-resolved measurements of microphases. Applications on geomaterials will be presented.

  15. Ultrafast optical responses of {beta}-carotene and lycopene probed by sub-20-fs time-resolved coherent spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, M.; Sugisaki, M. [CREST-JST and Department of Physics, Osaka City University, Osaka 558-8585 (Japan); Gall, A.; Robert, B. [CEA, Institut de Biologie et Technologies de Saclay, and CNRS, Gif-sur-Yvette F-91191 (France); Cogdell, R.J. [IBLS, Glasgow Biomedical Research Centre, University of Glasgow, Glasgow G12 8QQ, Scotland (United Kingdom); Hashimoto, H., E-mail: hassy@sci.osaka-cu.ac.j [CREST-JST and Department of Physics, Osaka City University, Osaka 558-8585 (Japan)

    2009-12-15

    We investigate how structural distortions in carotenoid cause decoherences of its high-frequency vibrational modes by applying the sub-20-fs time-resolved transient grating spectroscopy to {beta}-carotene and lycopene. The results indicate that the C=C central stretching mode shows significant loss of coherence under the effects of the steric hindrance between {beta}-ionone ring and polyene backbone, whereas the other high-frequency modes do not show such dependency on the structural distortions.

  16. Direct measurement of S-branch N2-H2 Raman linewidths using time-resolved pure rotational coherent anti-Stokes Raman spectroscopy.

    Science.gov (United States)

    Bohlin, A; Nordström, E; Patterson, B D; Bengtsson, P-E; Kliewer, C J

    2012-08-21

    S-branch N(2)-H(2) Raman linewidths have been measured in the temperature region 294-1466 K using time-resolved dual-broadband picosecond pure rotational coherent anti-Stokes Raman spectroscopy (RCARS). Data are extracted by mapping the dephasing rates of the CARS signal temporal decay. The J-dependent coherence decays are detected in the time domain by following the individual spectral lines as a function of probe delay. The linewidth data set was employed in spectral fits of N(2) RCARS spectra recorded in binary mixtures of N(2) and H(2) at calibrated temperature conditions up to 661 K using a standard nanosecond RCARS setup. In this region, the set shows a deviation of less than 2% in comparison with thermocouples. The results provide useful knowledge for the applicability of N(2) CARS thermometry on the fuel-side of H(2) diffusion flames. PMID:22920115

  17. Characterization of hydroxyapatite by time-resolved luminescence and FTIR spectroscopy

    Science.gov (United States)

    Grigorjeva, L.; Millers, D.; Smits, K.; Jankovica, Dz; Pukina, L.

    2013-12-01

    Time-resolved luminescence and FTIR absorption spectra of undoped and Eu and Ce doped hydroxyapatite nanocrystalline powders prepared by sol-gel method were studied. The luminescence band at 350-400 nm was detected and two decay times (11 ns and 38 ns) was determinated for Ce doped samples. The luminescence spectra and decay kinetics were analized for Eu doped nanopowders. The Eu3+ ion was incorporated in different Ca sites. The process of energy transfer to Eu3+ excited state (5D0) was detected from luminescence decay kinetics.

  18. Characterization of hydroxyapatite by time-resolved luminescence and FTIR spectroscopy

    International Nuclear Information System (INIS)

    Time-resolved luminescence and FTIR absorption spectra of undoped and Eu and Ce doped hydroxyapatite nanocrystalline powders prepared by sol-gel method were studied. The luminescence band at 350–400 nm was detected and two decay times (11 ns and 38 ns) was determinated for Ce doped samples. The luminescence spectra and decay kinetics were analized for Eu doped nanopowders. The Eu3+ ion was incorporated in different Ca sites. The process of energy transfer to Eu3+ excited state (5D0) was detected from luminescence decay kinetics

  19. Gridded Ionization Chambers for Time Resolved X-Ray Absorption Spectroscopy

    International Nuclear Information System (INIS)

    Common parallel plate ionization chambers are bandwidth limited by the ion drift velocity. Therefore they can severely decrease the effective energy resolution of time resolved EXAFS or XANES spectra. We therefore developed gridded ionization chambers which suppress the ionic component of the ionization current, which results in a substantial improvement of its bandwidth of typically two orders of magnitude. The rise time of these chambers is measured to be less than 5.5 μs. We have investigated the step response of parallel plate and gridded ionization chambers and discuss their influence on QEXAFS spectra.

  20. Ultrafast dynamics of o-fluorophenol studied with femtosecond time-resolved photoelectron and photoion spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The ultrafast dynamics of o-fluorophenol via the excited states has been studied by femtosecond time-resolved photoelectron imaging. The photoion and photoelectron spectra taken with a time delay between 267 nm pump laser and 800 nm probe laser provide a longer-lived S1 electronic state of about ns timescale. In comparison,the spectra obtained by exciting the S2 state with femtosecond laser pulses at 400 nm and ionizing with pulses at 800 nm suggest that the S2 state has an ultrashort lifetime about 102 fs and reflects the internal conversion dynamics of the S2 state to the S1 state.

  1. Time-resolved nonlinear polarization spectroscopy for measuring transient absorption and refraction in isotropic materials

    Science.gov (United States)

    Taranenko, Victor B.; Bazhenov, Vladimir Y.; Kulikovskaya, Olga A.

    1995-11-01

    A novel time-resolved nonlinear spectroscopic technique is described, which is based on stroboscopic registration of optical polarization transformation taking place at a vector incoherent two-wave mixing interaction in a modified Mach-Zehnder interferometer. It allows an accurate measuring of the dynamics of excitation and relaxation for real and imaginary parts of complex nonlinearity tensor components. The technique is demonstrated for measuring the light-induced change of transient absorption (delta) (alpha) e(t), (delta) (alpha) o(t) and refraction (delta) ne(t), (delta) no(t) for bacteriorhodopsin- based film pumped by linearly polarized laser pulses.

  2. Proceedings of the Thirteenth International Conference on Time-Resolved Vibrational Spectroscopy

    OpenAIRE

    Laubereau, Alfred; Mantel, Karl-Heinz; Zinth, Wolfgang

    2007-01-01

    The thirteenth meeting in a long-standing series of “Time-Resolved Vibrational Spectroscopy” (TRVS) conferences was held May 19th to 25th at the Kardinal Döpfner Haus in Freising, Germany, organized by the two Munich Universities - Ludwig-Maximilians-Universität and Technische Universität München. This international conference continues the illustrious tradition of the original in 1982, which took place in Lake Placid, NY. The series of meetings was initiated by leading, world-renowned exp...

  3. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    International Nuclear Information System (INIS)

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%–20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms

  4. Radiative lifetime measurements for some levels in Mn I and Ni I by time-resolved laser spectroscopy

    International Nuclear Information System (INIS)

    Natural radiative lifetimes for 32 excited levels of Mn I and for 17 excited levels of Ni I were measured using time-resolved laser-induced fluorescence (TR-LIF) spectroscopy in laser-induced plasma. The energy regions are from 45,754.27 to 54,950.81 cm−1 for Mn I and from 28,578.018 to 50,851.199 cm−1 for Ni I. The uncertainties of all lifetime results are within 10%. To our best knowledge, 26 lifetime results of Mn I and 9 lifetime results of Ni I are reported for the first time. - Highlights: • The experimental lifetimes of some Mn I and Ni I levels were obtained by time-resolved laser induced fluorescence method. • Radiative lifetimes of 26 energy levels in Mn I were reported for the first time. • Radiative lifetimes of 9 energy levels in Ni I were reported for the first time

  5. Analysis of hydrocarbon-bearing fluid inclusions (HCFI) using time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Przyjalgowski, Milosz A.; Ryder, Alan G.; Feely, Martin; Glynn, Thomas J.

    2005-06-01

    Hydrocarbon-bearing fluid inclusions (HCFI) are microscopic cavities within rocks that are filled with petroleum oil, the composition of which may not have changed since the trapping event. Thus, the composition of that entrapped oil can provide information about the formation and evolution of the oil reservoir. This type of information is important to the petroleum production and exploration industries. Crude oil fluorescence originates from the presence of cyclic aromatic compounds and the nature of the emission is governed by the chemical composition of the oil. Fluorescence based methods are widely used for analysis of crude oil because they offer robust, non-contact and non-destructive measurement options. The goal of our group is the development of a non-destructive analytical method for HCFI using time-resolved fluorescence methods. In broad terms, crude oil fluorescence behavior is governed by the concentration of quenching species and the distribution of fluorophores. For the intensity averaged fluorescence lifetime, the best correlations have been found between polar or alkane concentrations, but these are not suitable for robust, quantitative analysis. We have recently started to investigate another approach for characterizing oils by looking at Time-resolved Emission Spectra (TRES). TRES are constructed from intensities sampled at discrete times during the fluorescence decay of the sample. In this study, TRES, from a series of 10 crude oils from the Middle East, have been measured at discrete time gates (0.5 ns, 1 ns, 2 ns, 4 ns) over the 450-700 nm wavelength range. The spectral changes in TRES, such as time gate dependent Stokes' shift and spectral broadening, are analyzed in the context of energy transfer rates. In this work, the efficacy of using TRES for fingerprinting individual oils and HCFI is also demonstrated.

  6. Cerebral and Muscle Tissue Oxygenation During Incremental Cycling in Male Adolescents Measured by Time-Resolved Near-Infrared Spectroscopy.

    Science.gov (United States)

    Ganesan, Goutham; Leu, Szu-Yun; Cerussi, Albert; Tromberg, Bruce; Cooper, Dan M; Galassetti, Pietro

    2016-05-01

    Near-infrared spectroscopy has long been used to measure tissue-specific O2 dynamics in exercise, but most published data have used continuous wave devices incapable of quantifying absolute Hemoglobin (Hb) concentrations. We used time-resolved near-infrared spectroscopy to study exercising muscle (Vastus Lateralis, VL) and prefrontal cortex (PFC) Hb oxygenation in 11 young males (15.3 ± 2.1 yrs) performing incremental cycling until exhaustion (peak VO2 = 42.7 ± 6.1 ml/min/kg, mean peak power = 181 ± 38 W). Time-resolved near-infrared spectroscopy measurements of reduced scattering (μs´) and absorption (μa) at three wavelengths (759, 796, and 833 nm) were used to calculate concentrations of oxyHb ([HbO2]), deoxy Hb ([HbR]), total Hb ([THb]), and O2 saturation (stO2). In PFC, significant increases were observed in both [HbO2] and [HbR] during intense exercise. PFC stO2% remained stable until 80% of total exercise time, then dropped (-2.95%, p = .0064). In VL, stO2% decreased until peak time (-6.8%, p = .01). Segmented linear regression identified thresholds for PFC [HbO2], [HbR], VL [THb]. There was a strong correlation between timing of second ventilatory threshold and decline in PFC [HbO2] (r = .84). These findings show that time-resolved near-infrared spectroscopy can be used to study physiological threshold phenomena in children during maximal exercise, providing insight into tissue specific hemodynamics and metabolism. PMID:26451845

  7. Time-resolved two-photon excitation fluorescence spectroscopy and microscopy using a high repetition rate streak camera

    Institute of Scientific and Technical Information of China (English)

    LIU Li-xin; QU Ju-le; LIN Zi-yang; WANG Lei; FU Zhe; GUO Bao-ping; NIU Han-ben

    2007-01-01

    We present a time-resolved two-photon excitation fluorescence spectroscopy and a simultaneous time- and spectrumresolved multifocal multiphoton microscopy system that is based on a high repetition rate picosecond streak camera for providing time- and spectrum- resolved measurement and imaging in biomedicine. The performance of the system is tested and characterized by the fluorescence spectrum and lifetime analysis of several standard fluorescent dyes and their mixtures.Spectrum-resolved fluorescence lifetime images of fluorescence beads are obtained. Potential applications of the system include clinical diagnostics and cell biology etc.

  8. Time-resolved fluorescence spectroscopy of matrix-isolated silver atoms after pulsed excitation of inner-shell transitions

    Science.gov (United States)

    Hebert, T.; Wiggenhauser, H.; Schriever, U.; Kolb, D. M.

    1990-02-01

    The energy dissipation in matrix-isolated silver atoms after pulsed vacuum ultraviolet (VUV) excitation of 4d-5p transitions has been studied by time-resolved fluorescence spectroscopy. The decay behavior of the various fluorescence bands has been analyzed and a model for the relaxation process proposed within the framework of a two-dimensional configuration-coordinate diagram. If minute quantities of Ag2 are present in the matrix, the analysis requires consideration of energy transfer between silver atoms and dimers.

  9. Time-resolved absorption spectroscopy of optically pumped Si by using fs-laser plasma x-ray

    International Nuclear Information System (INIS)

    Femtosecond laser-produced plasmas emit ultrashort x-ray pulse that is synchronized to a femtosecond laser pulse. By utilizing this feature, we demonstrated time-resolved soft x-ray absorption measurements of optically pumped silicon near its LII,III absorption edge by means of pump-probe spectroscopy. As a result, we observed more than 10% increase in the absorption near absorption edge caused by laser pulse irradiation, which means that the transition of core-electrons was rapidly modified by excitation of valence electrons. The recovery time constant of this change was measure to be about 20 ps. (author)

  10. Probing Reaction Dynamics of Transition-Metal Complexes in Solution via Time-Resolved X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils; Khalil, Munira; Kim, Tae Kyu; Smeigh, Amanda L.; Jamula, Lindsey; McCusker, James K.; Schoenlein, Robert W.

    2009-05-24

    We report measurements of the photo-induced Fe(II) spin crossover reaction dynamics in solution via time-resolved x-ray absorption spectroscopy. EXAFS measurements reveal that the iron?nitrogen bond lengthens by 0.21+-0.03 Angstrom in the high-spin transient excited state relative to the ground state. XANES measurements at the Fe L-edge show directly the influence of the structural change on the ligand-field splitting of the Fe(II) 3d orbitals associated with the spin transition.

  11. Probing reaction dynamics of transition-metal complexes in solution via time-resolved X-ray spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils [Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1Cyclotron Road, Berkeley, CA 94720 (United States); Khalil, Munira [Department of Chemistry, University of Washington, Seattle, WA 98195 (United States); Kim, Tae Kyu [Department of Chemistry, Pusan National University, Busan 609-735 (Korea, Republic of); Smeigh, Amanda L; Jamula, Lindsey; McCusker, James K [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Schoenlein, Robert W, E-mail: nhuse@lbl.go, E-mail: rwschoenlein@lbl.go [Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA (United States)

    2009-02-01

    We report measurements of the photoinduced Fe{sup II} spin crossover reaction dynamics in solution via time-resolved x-ray absorption spectroscopy. EXAFS measurements reveal that the iron-nitrogen bond lengthens by 0.21+-0.03 A in the high-spin transient excited state relative to the ground state. XANES measurements at the Fe L-edge show directly the influence of the structural change on the ligand-field splitting of the Fe{sup II} 3d orbitals associated with the spin transition.

  12. Charge transport and localization in nanocrystalline CdS films: A time-resolved terahertz spectroscopy study

    Czech Academy of Sciences Publication Activity Database

    Mics, Zoltan; Němec, Hynek; Rychetský, Ivan; Kužel, Petr; Formánek, P.; Malý, P.; Němec, P.

    2011-01-01

    Roč. 83, č. 15 (2011), "155326-1"-"155326-6". ISSN 1098-0121 R&D Projects: GA ČR GD202/09/H041; GA ČR(CZ) GP202/09/P099; GA ČR GA202/09/0430; GA MŠk LC512; GA AV ČR(CZ) IAA100100902 Institutional research plan: CEZ:AV0Z10100520 Keywords : time-resolved THz spectroscopy * CdS nanoparticles * electron transport * chemical bath deposition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.691, year: 2011

  13. Time-resolved fluorescence spectroscopy for intraoperative assistance of thyroid surgery

    Science.gov (United States)

    Bachmann, L.; Brandao, M. P.; Iwakura, R.; Basilio, F. S.; Haleplian, K.; Ito, A. S.; Conti de Freitas, L. C.

    2016-03-01

    Searching for new methods to provide information of biochemical composition and structure is critical to improve the prognosis of thyroid diseases. The use of time-resolved fluorescence techniques to detect biochemical composition and tissue structure alterations could help develop a portable, minimally invasive, and non-destructive method to assist during surgical procedures. This research looks for employ a fluorescence technique based on lifetime measurements to differentiate healthy and benign lesions from malignant thyroid tissue. We employ a wide range of excitation and chose a more appropriate region for this work: 298-300 nm; and the fluorescence decay was measured at 340-450 nm. We observed fluorescence lifetimes at 340 nm emission of 0.80+/-0.26 and 3.94+/-0.47 ns for healthy tissue; 0.90+/-0.24 and 4.05+/-0.46 ns for benign lesions; and 1.21+/-0.14 and 4.63+/-0.25 ns for malignant lesions. For 450 nm emissions, we obtain lifetimes of 0.25+/-0.18 and 3.99+/-0.39 ns for healthy tissue, 0.24+/-0.17 and 4.20+/-0.48 ns for benign lesions, 0.33+/-0.32 and 4.55+/-0.55 ns for malignant lesions. We successfully demonstrated that fluorescence lifetimes at 340 nm emission can differentiate between thyroid malignant and healthy/benign tissues.

  14. TIME-RESOLVED SPECTROSCOPY OF THE POLAR EU CANCRI IN THE OPEN CLUSTER MESSIER 67

    International Nuclear Information System (INIS)

    We present time-resolved spectroscopic and polarimetric observations of the AM Her system EU Cnc. EU Cnc is located near the core of the old open cluster Messier 67; new proper motion measurements indicate that EU Cnc is indeed a member of the star cluster, and this system therefore is useful to constrain the formation and evolution of magnetic cataclysmic variables. The spectra exhibit two-component emission features with independent radial velocity variations as well as time-variable cyclotron emission indicating a magnetic field strength of 41 MG. The period of the radial velocity and cyclotron hump variations are consistent with the previously known photometric period, and the spectroscopic flux variations are consistent in amplitude with previous photometric amplitude measurements. The secondary star is also detected in the spectrum. We also present polarimetric imaging measurements of EU Cnc that show a clear detection of polarization, and the degree of polarization drops below our detection threshold at phases when the cyclotron emission features are fading or not evident. The combined data are all consistent with the interpretation that EU Cnc is a low-state polar in the cluster Messier 67. The mass function of the system gives an estimate of the accretor mass of MWD ≥ 0.68 M☉ with MWD ≈ 0.83 M☉ for an average inclination. We are thus able to place a lower limit on the progenitor mass of the accreting white dwarf of ≥1.43 M☉.

  15. Multiplexed measurements by time resolved spectroscopy using colloidal CdSe/ZnS quantum dots

    International Nuclear Information System (INIS)

    Multiplexed measurements of analytes in parallel is a topical demand in bioanalysis and bioimaging. An interesting alternative to commonly performed spectral multiplexing is lifetime multiplexing. In this Letter, we present a proof of principle of single-color lifetime multiplexing by coupling the same fluorophore to different nanoparticles. The effective lifetime of the fluorophores can be tuned by more than one order of magnitude due to resonance energy transfer from donor states. Measurements have been done on a model systems consisting of ATTO-590 dye molecules linked to either gold particles or to CdSe/ZnS core shell quantum dots. Both systems show the same luminescence spectrum of ATTO-590 dye emission in continuous wave excitation, but can be distinguished by means of time resolved measurements. The dye molecules bound to gold particles exhibit a mono-exponential decay with a lifetime of 4.5 ns, whereas the dye molecules bound to CdSe/ZnS dots show a nonexponential decay with a slow component of about 135 ns due to the energy transfer from the quantum dots. We demonstrate the fundamental possibility to determine the mixing ratio for dyes with equal luminescence spectra but very different transients. This opens up a pathway independent of the standard optical multiplexing with many different fluorophores emitting from the near ultraviolet to the near infrared spectral region

  16. Time-Resolved HST Spectroscopy of Four Eclipsing Magnetic Cataclysmic Variables

    CERN Document Server

    Schmidt, G D; Schmidt, Gary D.

    2000-01-01

    Time-resolved HST UV eclipse spectrophotometry is presented for the magnetic CVs V1309 Ori, MN Hya, V2301 Oph, and V1432 Aql. Separation of the light curves into wavebands allows the multiple emission components to be distinguished. Photospheric hot spots are detected in V1309 Ori and V2301 Oph. The emission- line spectra of V1309 Ori and MN Hya are unusual, with the strength of N V 1240 and N IV 1718 suggesting an overabundance of nitrogen. Three epochs of observation of the asynchronous V1432 Aql cover ~1/3 of a 50-day lap cycle between the white dwarf spin and binary orbit. The light curves vary from epoch to epoch and as a function of waveband. The dereddened UV spectrum is extremely bright and the spectral energy distribution coupled with the duration of eclipse ingress indicate that the dominant source of energy is a hot (T~35,000K) white dwarf. Undiminished line emission through eclipse indicates that the eclipse is caused by the accretion stream, not the secondary star. The hot white dwarf, combined w...

  17. Theory of spin dynamics of magnetic adatoms traced by time-resolved scanning tunneling spectroscopy

    CERN Document Server

    Schüler, Michael; Berakdar, Jamal

    2012-01-01

    The inelastic scanning tunneling microscopy (STM) has been shown recently (Loth et al. Science 329, 1628 (2010)) to be extendable as to access the nanosecond, spin-resolved dynamics of magnetic adatoms and molecules. Here we analyze theoretically this novel tool by considering the time-resolved spin dynamics of a single adsorbed Fe atom excited by a tunneling current pulse from a spin-polarized STM tip. The adatom spin-configuration can be controlled and probed by applying voltage pulses between the substrate and the spin-polarized STM tip. We demonstrate how, in a pump-probe manner, the relaxation dynamics of the sample spin is manifested in the spin-dependent tunneling current. Our model calculations are based on the scattering theory in a wave-packet formulation. The scheme is nonpertubative and hence, is valid for all voltages. The numerical results for the tunneling probability and the conductance are contrasted with the prediction of simple analytical models and compared with experiments.

  18. Diffusion optical spectroscopy of cancerous and normal prostate tissues in time-resolved and frequency domain

    Science.gov (United States)

    Zhou, Kenneth J.; Pu, Yang; Chen, Jun

    2014-03-01

    It is well-known that light transport can be well described using Maxwell's electromagnetic theory. In biological tissue, the scattering particles cause the interaction of scattered waves from neighboring particles. Since such interaction cannot be ignored, multiple scattering occurs. The theoretical solution of multiple scattering is complicated. A suitable description is that the wavelike behavior of light is ignored and the transport of an individual photon is considered to be absorbed or scattered. This is known as the Radiative Transfer Equation (RTE) theory. Analytical solutions to the RTE that explicitly describes photon migration can be obtained by introducing some proper approximations. One of the most popular models used in the field of tissue optics is the Diffusion Approximation (DA). In this study, we report on the results of our initial study of optical properties of ex vivo normal and cancerous prostate tissues and how tissue parameters affect the near infrared light transporting in the two types of tissues. The time-resolved transport of light is simulated as an impulse isotropic point source of energy within a homogeneous unbounded medium with different absorption and scattering properties of cancerous and normal prostate tissues. Light source is also modulated sinusoidally to yield a varied fluence rate in frequency domain at a distant observation point within the cancerous and normal prostate tissues. Due to difference of the absorption and scattering coefficients between cancerous and normal tissues, the expansion of light pulse, intensity, phase are found to be different.

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

    Science.gov (United States)

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

    2007-05-01

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

  20. Time-resolved spectroscopy of alkali clusters in the pico- and femtosecond time domain

    International Nuclear Information System (INIS)

    The wave packet propagation and fragmentation dynamics of small potassium and sodium clusters in a supersonic cluster beam had been investigated using pico- and femtosecond two-photon-ionization spectroscopy followed by mass-selective detection. (author)

  1. Femtosecond time-resolved absorption spectroscopy of astaxantin in solution and in alpha-crustacyanin

    Czech Academy of Sciences Publication Activity Database

    Ilagan, R.P.; Christensen, R.L.; Chapp, T.W.; Frank, H.A.; Polívka, Tomáš; Pascher, T.

    2005-01-01

    Roč. 109, č. 14 (2005), s. 3120-3127. ISSN 1089-5639 Institutional research plan: CEZ:AV0Z50510513 Keywords : absorption spectroscopy * astaxantin Subject RIV: BO - Biophysics Impact factor: 2.898, year: 2005

  2. X-ray Crystal Structure and Time-resolved Spectroscopy of the Blue Carotenoid Violerythrin

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Frank, H.A.; Enriquez, M.M.; Niedzwiedzki, D.M.; Liaaen-Jensen, S.; Hemming, J.; Helliwell, J.R.; Helliwell, M.

    2010-01-01

    Roč. 114, č. 26 (2010), s. 8760-8769. ISSN 1520-6106 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited states * spectroscopy Subject RIV: BO - Biophysics Impact factor: 3.603, year: 2010

  3. Laser-induced time-resolved spectroscopy of visible broad luminescence bands in zircon

    International Nuclear Information System (INIS)

    This work examines the luminescence of zircon studied by laser-induced time-resolved methods. This method allows the differentiation between luminescence centers of similar emission wavelengths, but different decay times. Samples include a suite of natural zircons, nominally pure synthetic ZrSiO4, and ZrSiO4 artificially doped by Mn, Fe, Cr, Ni, Co, Pb, Sb, Ti, Ta, V, Sc, U, U-P, and Th-P. In addition, pure ZrSiO4 samples irradiated by thermal neutrons have been studied. We have clarified the nature of several luminescence bands reported previously from time independent studies, and suggest the following as the causes of luminescence in zircon systems: 1) the yellow band with peak wavelength (λmax) = 575 nm, peak half-width (Δ) = 120-130 nm, and decay time (τ) = 30-35 μs is connected with neutron and alpha irradiation, 2) the green band with λmax 505 nm, and vibrational structure is linked to the presence of the uranyl ion, but it is only observed in artificial samples with co-doping by U and P, 3) the red band with λmax = 750 nm, Δ =110-120 nm and τ 3-5 ms is connected with Fe3+. We have also identified new luminescence bands, obscured by stronger emissions. These are: emission a) with λmax 480 nm, Δ = 70-80 nm and τ = 300-325 μs, emission b) with λmax = 515 nm, Δ = 90-100 nm and τ 500-520 gs, emission c) with λmax = 605 nm, Δ = 110-125 nm and τ = 8-10 μs. These emissions have not been detected in synthetic doped zircons and their interpretation remains the subject of further investigation. (author)

  4. Quantitative measurement of optical parameters in normal breasts using time-resolved spectroscopy: in vivo results of 30 Japanese women

    Science.gov (United States)

    Suzuki, Kazunori; Yamashita, Yutaka; Ohta, Kazuyoshi; Kaneko, Masao; Yoshida, Masayuki; Chance, Britton

    1996-07-01

    Previous investigation has proved time-resolved spectroscopy to be applicable to measurement of optical parameters in the human breast. To increase knowledge of these properties in vivo, the optical parameters of healthy breasts were measured using time-resolved reflectance spectroscopy. A time-correlated single-photon counting method was used to obtain time-response curves for the breasts of 30 Japanese women. Values of (mu) a and (mu) s$' were analyzed by fitting the curves to the diffusion equation. The relationships of optical parameters to age, body mass index, thickness of the breast, number of pregnancies, and menstrual status were examined. The (mu) a and (mu) s' ranged from 0.0024 to 0.0078/mm and from 0.63 to 1.08/mm, respectively. The values of (mu) a and (mu) s' showed a high correlation with properties may be strongly influenced by changes in tissue components related to aging, menstrual status, and so on. This optical information will contribute to the investigation of photon migration in the human breast.

  5. Rate constant of exciton quenching of Ir(ppy)3 with hole measured by time-resolved luminescence spectroscopy

    Science.gov (United States)

    Oyama, Shiho; Sakai, Heisuke; Murata, Hideyuki

    2016-03-01

    We observed the quenching of tris(2-phenylpyridinato)iridium(III) [Ir(ppy)3] excitons by polarons (holes or electrons) by time-resolved photoluminescence (PL) spectroscopy to clarify the dynamics of the triplet-polaron quenching of excitons. We employed a hole-only device (HOD) and an electron-only device (EOD), where the emitting layer consists of Ir(ppy)3 doped in 4,4‧-bis(carbazol-9-yl)biphenyl. Time-resolved PL spectroscopy of the EOD and HOD were measured under a constant current density. The results showed that the excitons of Ir(ppy)3 were significantly quenched only by holes. The PL decay curves of HOD were well fitted by the biexponential function, where lifetimes (τ1 and τ2) remain unchanged but the coefficient of each exponential term depends on hole current density. From the results, we proposed a model of exciton quenching where the exciton-hole quenching area expands with increasing hole current density. On the basis of the model, the triplet-polaron quenching rate constant Kq was determined.

  6. Time-resolved laser spectroscopy in the UV/VUV spectral region

    International Nuclear Information System (INIS)

    Radiative lifetimes ranging from 3 to 500 ns were measured on various states of Ag, N, Se, Te and As, by recording the fluorescence light decay after excitation by a laser pulse. Ag was supplied by a collimated atomic beam while Se, Te and As were contained in quartz cells. Pulsed laser radiation, with a wavelength down to 185 nm, was generated by different set-ups, using Nd-YAG pumped dye lasers combined with non-linear crystals and Raman shifting. Short laser pulses were produced by a nitrogen laser or a distributed feedback dye laser. Two-photon processes and stepwise excitation were used to populate high-lying levels. Depletion spectroscopy, quantum-beat spectroscopy and optical double resonance spectroscopy were also performed

  7. New methods and applications in time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Recent experimental advances and developments in the QEXAFS technique were presented along with new applications in the disciplines of catalysis and surface science. Both performance and user-friendliness of the QEXAFS method were significantly improved, while the applicability of QEXAFS was extended by newly designed mechanics. The application of a fast angular encoder proved to be capable to sample the continuously changing Bragg angle of the monochromator crystal synchronized to the acquired absorption data. A new data acquisition system was designed, based on a multifunctional ADC board, which provides high acquisition frequencies, while low noise acquisition could be achieved due to the provided differential acquisition mode. Additionally, control of all experimental devices as current amplifiers, monochromator motors and sample stages were implemented to further increase the efficiency of the experimental setup for QEFAS measurements. In order to simplify the processing of the huge generated QEXAFS raw data files, a completely new software tool for data analysis was designed, which provides not only the basic procedures of QEXAFS data analysis, but also many approaches customized for time-resolved data. Apart from technical advances, various experiments were performed with QEXAFS to gain new insights into the complex processes of several catalytic reactions, the thermal decomposition of metal oxalates, as well as layer growth processes and reactions on rough surfaces. Supported Pd catalysts were investigated during catalytic partial oxidation of methane, whereby oscillations in the conversion were linked to structural changes of the catalyst. Kinetic oscillations were also investigated on a supported Pt catalyst during the extinction of CO oxidation induced by decreasing temperature. Modulated experiments were investigated (i) on supported Pt-Rh/Al2O3 catalysts during active catalytic partial oxidation in switching gas atmospheres of methane and hydrogen, and

  8. Ultrabroadband time-resolved THz spectroscopy of polymer-based solar cells

    DEFF Research Database (Denmark)

    Cooke, David G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2011-01-01

    We have developed ultrabroadband THz spectroscopy in reflection mode for characterization of conductivity dynamics in conductive polymer samples used in organic solar cells. The spectrometer is designed to have a time resolution limited only by the duration of the optical pump pulse, thus enabling...

  9. Atomic cesium 6h states observed by time-resolved FTIR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Kubelík, Petr; Jelínek, Petr; Chernov, V. E.; Knyazev, M. Yu.

    2011-01-01

    Roč. 44, č. 22 (2011), s. 225006. ISSN 0953-4075 R&D Projects: GA AV ČR IAA400400705 Institutional research plan: CEZ:AV0Z40400503 Keywords : cesium * FTIR spectroscopy * infrared emission spectra Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.875, year: 2011

  10. Microcontroller based resonance tracking unit for time resolved continuous wave cavity-ringdown spectroscopy measurements

    Czech Academy of Sciences Publication Activity Database

    Votava, Ondřej; Mašát, Milan; Parker, A. E.; Jain, Ch.; Fittschen, Ch.

    2012-01-01

    Roč. 83, č. 4 (2012), 043110. ISSN 0034-6748 R&D Projects: GA ČR GA203/09/0422 Institutional support: RVO:61388955 Keywords : CW-DIODE-LASER * DOWN SPECTROSCOPY * KINETICS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.602, year: 2012

  11. Hydrogen-bond lifetime measured by time-resolved 2D-IR spectroscopy: N-methylacetamide in methanol

    Science.gov (United States)

    Woutersen, S.; Mu, Y.; Stock, G.; Hamm, P.

    2001-05-01

    2D vibrational spectroscopy is applied to investigate the equilibrium dynamics of hydrogen bonding of N-methylacetamide (NMA) dissolved in methanol- d4. For this particular solute-solvent system, roughly equal populations are found for two conformers of the solute-solvent complex, one of which forms a hydrogen bond from the CO group of NMA to the surrounding solvent, and one of which does not. Using time-resolved 2D-IR spectroscopy on the amide I band of NMA, the exchange between both conformers is resolved. Equilibration of each conformer is completed after 4.5 ps, while the formation and breaking of the hydrogen bond occurs on a slower, 10-15 ps time scale. This interpretation is supported by classical molecular-dynamics simulations of NMA in methanol. The calculations predict a 64% population of the hydrogen-bonded conformer and an average hydrogen-bond lifetime of ≈12 ps.

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

    OpenAIRE

    Miaja-Avila, L.; G. C. O'Neil; Uhlig, J.; C. L. Cromer; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-01-01

    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 ∼106 photons/s, by focusing the produced x-rays with a polycapillary opti...

  13. In Situ Planetary Mineralogy Using Simultaneous Time Resolved Fluorescence and Raman Spectroscopy

    Science.gov (United States)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

    Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form it is one of the front runners for the next generation of in situ instruments designed to explore adverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for potential cache and return missions.

  14. Time resolved super continuum Cavity Ring-Down Spectroscopy for multicomponent gas detection

    International Nuclear Information System (INIS)

    In this work, we present a variation of the technique CRDS (Cavity Ring-Down Spectroscopy) to obtain simultaneously a multicomponent absorption spectrum in a broad visible range. This new approach uses the Supercontinuum (SC) spectrum (resulting from irradiation of nonlinear media by femtosecond lasers, or simply generated by compact sources) as a light source to illuminate the cavity. In this context it is described the features of the modules assembling a MC-SC-CRDS (Multicomponent Supercontinuum Cavity Ring-Down Spectroscopy): a set of high reflectivity mirrors, the resonant cavity and the detection system. Some problems related to the multimode excitation, stray light, effective use of the dynamic range of the detector, the poor resolution of the instrument to resolve narrow absorption lines are issued. We present the absorption spectra of H2O (polyads 4υ, 4υ + δ) and O2 (spin-forbidden b-X branch) measured simultaneously by this technique in the visible range and a comparison with the absorption lines based on HITRAN database is made to demonstrate the functionality of this method. (author)

  15. Retrieval procedure for time-resolved near-infrared tissue spectroscopy based on the optimal estimation method

    International Nuclear Information System (INIS)

    We propose the use of a retrieval procedure for time-resolved near-infrared tissue spectroscopy based on the ‘optimal estimation’ method. The aim of this retrieval method is to obtain an improved estimate of the target parameters compared with standard nonlinear least-squares routines, since the inverse problem dedicated to retrieve the optical properties of tissue is ill posed. A priori information on target and forward model parameters is used, so that a larger number of target parameters can be retrieved, and/or a better accuracy and precision can be achieved on the retrieved target parameters. The procedure has been tested on time-resolved simulated experiments generated, using solutions of the diffusion equation and with solutions of the radiative transfer equation reconstructed with Monte Carlo simulations. The results obtained show that, by using a priori information on target parameters, we have a smaller difference between retrieved values and true values, and lower retrieved error bars. Similarly, a more correct estimate of the errors of the forward model parameters improves the retrieval of the target parameters. (paper)

  16. The H + OCS hot atom reaction - CO state distributions and translational energy from time-resolved infrared absorption spectroscopy

    Science.gov (United States)

    Nickolaisen, Scott L.; Cartland, Harry E.

    1993-01-01

    Time-resolved infrared diode laser spectroscopy has been used to probe CO internal and translational excitation from the reaction of hot H atoms with OCS. Product distributions should be strongly biased toward the maximum 1.4 eV collision energy obtained from 278 nm pulsed photolysis of HI. Rotations and vibrations are both colder than predicted by statistical density of states theory, as evidenced by large positive surprisal parameters. The bias against rotation is stronger than that against vibration, with measurable population as high as v = 4. The average CO internal excitation is 1920/cm, accounting for only 13 percent of the available energy. Of the energy balance, time-resolved sub-Doppler line shape measurements show that more than 38 percent appears as relative translation of the separating CO and SH fragments. Studies of the relaxation kinetics indicate that some rotational energy transfer occurs on the time scale of our measurements, but the distributions do not relax sufficiently to alter our conclusions. Vibrational distributions are nascent, though vibrational relaxation of excited CO is unusually fast in the OCS bath, with rates approaching 3 percent of gas kinetic for v = 1.

  17. Natural Lifetimes of Excited-states of Neutral Nitrogen Determined By Time-resolved Laser Spectroscopy

    OpenAIRE

    Bengtsson, G. J; Larsson, Jörgen; Svanberg, Sune; Wang, D. D

    1992-01-01

    Radiative lifetimes were determined for three quartet states of neutral nitrogen, and sequences of Rydberg states were studied using depletion spectroscopy. Free nitrogen atoms were generated by photodissociation of N2O using frequency-tripled dye-laser radiation that was two-photon resonant with the 2p(2)3p 4S or 4D states. Further quartet states were reached by a subsequent single-photon absorption. We obtain tau(2p(2)3p 4D7/2) = 44(2) ns, tau(2p(2)3p 4S3/2) = 26.0(1.5) ns, and tau(2p(2)6s4...

  18. Picosecond time-resolved X-ray absorption spectroscopy of ultrafast aluminum plasmas.

    Science.gov (United States)

    Audebert, P; Renaudin, P; Bastiani-Ceccotti, S; Geindre, J-P; Chenais-Popovics, C; Tzortzakis, S; Nagels-Silvert, V; Shepherd, R; Matsushima, I; Gary, S; Girard, F; Peyrusse, O; Gauthier, J-C

    2005-01-21

    We have used point-projection K-shell absorption spectroscopy to infer the ionization and recombination dynamics of transient aluminum plasmas. Two femtosecond beams of the 100 TW laser at the LULI facility were used to produce an aluminum plasma on a thin aluminum foil (83 or 50 nm), and a picosecond x-ray backlighter source. The short-pulse backlighter probed the aluminum plasma at different times by adjusting the delay between the two femtosecond driving beams. Absorption x-ray spectra at early times are characteristic of a dense and rather homogeneous plasma. Collisional-radiative atomic physics coupled with hydrodynamic simulations reproduce fairly well the measured average ionization as a function of time. PMID:15698184

  19. Real-Time Probing of Electron Dynamics Using Attosecond Time-Resolved Spectroscopy

    Science.gov (United States)

    Ramasesha, Krupa; Leone, Stephen R.; Neumark, Daniel M.

    2016-05-01

    Attosecond science has paved the way for direct probing of electron dynamics in gases and solids. This review provides an overview of recent attosecond measurements, focusing on the wealth of knowledge obtained by the application of isolated attosecond pulses in studying dynamics in gases and solid-state systems. Attosecond photoelectron and photoion measurements in atoms reveal strong-field tunneling ionization and a delay in the photoemission from different electronic states. These measurements applied to molecules have shed light on ultrafast intramolecular charge migration. Similar approaches are used to understand photoemission processes from core and delocalized electronic states in metal surfaces. Attosecond transient absorption spectroscopy is used to follow the real-time motion of valence electrons and to measure the lifetimes of autoionizing channels in atoms. In solids, it provides the first measurements of bulk electron dynamics, revealing important phenomena such as the timescales governing the switching from an insulator to a metallic state and carrier-carrier interactions.

  20. Real-Time Probing of Electron Dynamics Using Attosecond Time-Resolved Spectroscopy.

    Science.gov (United States)

    Ramasesha, Krupa; Leone, Stephen R; Neumark, Daniel M

    2016-05-27

    Attosecond science has paved the way for direct probing of electron dynamics in gases and solids. This review provides an overview of recent attosecond measurements, focusing on the wealth of knowledge obtained by the application of isolated attosecond pulses in studying dynamics in gases and solid-state systems. Attosecond photoelectron and photoion measurements in atoms reveal strong-field tunneling ionization and a delay in the photoemission from different electronic states. These measurements applied to molecules have shed light on ultrafast intramolecular charge migration. Similar approaches are used to understand photoemission processes from core and delocalized electronic states in metal surfaces. Attosecond transient absorption spectroscopy is used to follow the real-time motion of valence electrons and to measure the lifetimes of autoionizing channels in atoms. In solids, it provides the first measurements of bulk electron dynamics, revealing important phenomena such as the timescales governing the switching from an insulator to a metallic state and carrier-carrier interactions. PMID:26980312

  1. Synthesis of Ag clusters in microemulsions: A time-resolved UV vis and fluorescence spectroscopy study

    Science.gov (United States)

    Ledo, Ana; Martínez, F.; López-Quintela, M. A.; Rivas, J.

    2007-09-01

    The combined use of the microemulsion technique and the kinetic control allows the preparation of small silver clusters. By using UV-vis and fluorescence spectroscopy the main stages by which the clusters grow, before the formation of nanoparticles, were elucidated. Transmission electron microscopy (TEM) and scanning tunnelling microscopy (STM) were used to further characterize the samples. Two main stages were clearly identified, which are associated with: (1) the formation of Ag n clusters with n<10, which self-aggregate into one atom high 2D nanodiscs of 3.2 nm size and (2) Ag n clusters, which self-aggregate into 3D nanostructures of 1.5 nm in size. The fluorescence properties observed with both stages show that the formed clusters are small enough to display a molecule-like behaviour.

  2. Diagnosis of laser ablated carbon particles measured by time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    The time and space resolved properties of laser ablated carbon particles were measured by X-ray absorption spectroscopy using LPX as an X-ray source. The energy density of the irradiation laser on the sample was in the range of 0.5-20J/cm2 and the time delay was varied between 0 and 120ns. The absorption spectra exhibited several peaks originated from level to level transitions and an intense broad absorption in the energy range of C-K edge. At a delay time of 120ns, the absorption peak from 1s→2p transition of neutral carbon atom (C0), C-, C+ and C2+ ions were observed. The absorption peak from C0 was stronger as the probing position was closer to the sample surface and decreased rapidly with distance from the sample surface. The absorption peak C2+ ion was observed only at comparatively distant positions from surface. The maximum speeds of highly charged ions were faster than that of neutral atoms and negative charged ions. The neutral atom and lower charged ions were emitted from the sample even after laser irradiation. The spatial distributions of the laser ablated carbon particles in the localized helium gas environment were measured. In the helium gas environment, the ablation plume was depressed by the helium cloud generated on the top of ablation plume. (author)

  3. Ultrafast XUV Pulses at High Repetition Rate for Time Resolved Photoelectron Spectroscopy of Surface Dynamics

    Science.gov (United States)

    Corder, Christopher; Zhao, Peng; Li, Xinlong; Muraca, Amanda R.; Kershis, Matthew D.; White, Michael G.; Allison, Thomas K.

    2016-05-01

    Ultrafast photoelectron studies of surface dynamics are often limited by low repetition rates. At Stony Brook we have built a cavity-enhanced high-harmonic generation XUV source that delivers ultrafast pulses to a surface science apparatus for photoelectron spectroscopy. We begin with a Ytterbium fiber laser at a repetition rate of 78 MHz and up to 90 W of average power. After compression the pulses have μJ's of energy with high harmonic generation. The enhancement cavity is a six mirror double folded bow-tie geometry with a focus of 15 μm at a Krypton gas jet, followed by a Sapphire crystal at Brewster's angle for the fundamental to allow outcoupling of the harmonics. A single harmonic is selected using a time-preserving monochromator to maintain the short pulses, and is sent to an ultra high vacuum chamber with sample preparation and diagnostic tools as well as an electron energy spectrometer. This allows us to study the electronic dynamics of semiconductor surfaces and their interfaces with adsorbed molecules which enable various charge transfer effects. Supported by AFOSR.

  4. Time-Resolved Spectroscopy Diagnostic of Laser-Induced Optical Breakdown

    International Nuclear Information System (INIS)

    Transient laser plasma is generated in laser-induced optical breakdown (LIOB). Here we report experiments conducted with 10.6-micron CO2 laser radiation, and with 1.064-micron fundamental, 0.532-micron frequency-doubled, 0.355-micron frequency-tripled Nd:YAG laser radiation. Characterization of laser induced plasma utilizes laser-induced breakdown spectroscopy (LIBS) techniques. Atomic hydrogen Balmer series emissions show electron number density of 1017 cm-3 measured approximately 10μs and 1μs after optical breakdown for CO2 and Nd:YAG laser radiation, respectively. Recorded molecular recombination emission spectra of CN and C2 Swan bands indicate an equilibrium temperature in excess of 7000 Kelvin, inferred for these diatomic molecules. Reported are also graphite ablation experiments where we use unfocused laser radiation that is favorable for observation of neutral C3 emission due to reduced C3 cation formation. Our analysis is based on computation of diatomic molecular spectra that includes accurate determination of rotational line strengths, or Honl-London factors

  5. Time-Resolved Spectroscopy Diagnostic of Laser-Induced Optical Breakdown

    Directory of Open Access Journals (Sweden)

    Christian G. Parigger

    2010-01-01

    Full Text Available Transient laser plasma is generated in laser-induced optical breakdown (LIOB. Here we report experiments conducted with 10.6-micron CO2 laser radiation, and with 1.064-micron fundamental, 0.532-micron frequency-doubled, 0.355-micron frequency-tripled Nd:YAG laser radiation. Characterization of laser induced plasma utilizes laser-induced breakdown spectroscopy (LIBS techniques. Atomic hydrogen Balmer series emissions show electron number density of 1017 cm−3 measured approximately 10 μs and 1 μs after optical breakdown for CO2 and Nd:YAG laser radiation, respectively. Recorded molecular recombination emission spectra of CN and C2 Swan bands indicate an equilibrium temperature in excess of 7000 Kelvin, inferred for these diatomic molecules. Reported are also graphite ablation experiments where we use unfocused laser radiation that is favorable for observation of neutral C3 emission due to reduced C3 cation formation. Our analysis is based on computation of diatomic molecular spectra that includes accurate determination of rotational line strengths, or Hönl-London factors.

  6. Time-resolved Ultraviolet Spectroscopy of the M-dwarf GJ 876 Exoplanetary System

    CERN Document Server

    France, Kevin; Tian, Feng; Froning, Cynthia S; Roberge, Aki

    2012-01-01

    Extrasolar planets orbiting M-stars may represent our best chance to discover habitable worlds in the coming decade. The ultraviolet spectrum incident upon both Earth-like and Jovian planets is critically important for proper modeling of their atmospheric heating and chemistry. In order to provide more realistic inputs for atmospheric models of planets orbiting low-mass stars, we present new near- and far-ultraviolet (NUV and FUV) spectroscopy of the M-dwarf exoplanet host GJ 876 (M4V). Using the COS and STIS spectrographs aboard the Hubble Space Telescope, we have measured the 1150-3140A spectrum of GJ 876. We have reconstructed the stellar HI LyA emission line profile, and find that the integrated LyA flux is roughly equal to the rest of the integrated flux (1150-1210A + 1220-3140A) in the entire ultraviolet bandpass (F(LyA)/F(FUV+NUV) ~0.7). This ratio is ~ 2500x greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H2 (T(H2) > ...

  7. Time-resolved x-ray absorption spectroscopy: Watching atoms dance

    International Nuclear Information System (INIS)

    The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 A. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

  8. Rebinding dynamics of NO to microperoxidase-8 probed by time-resolved vibrational spectroscopy.

    Science.gov (United States)

    Lee, Taegon; Kim, Jooyoung; Park, Jaeheung; Pak, Youngshang; Kim, Hyojoon; Lim, Manho

    2016-02-21

    Femtosecond vibrational spectroscopy was used to probe the rebinding kinetics of NO to microperoxidase-8 (Mp), an ideal model system for the active site of ligand-binding heme proteins, including myoglobin and hemoglobin, after the photodeligation of MpNO in glycerol/water (G/W) solutions at 294 K. The geminate rebinding (GR) of NO to Mp in viscous solutions was highly efficient and ultrafast and negligibly dependent on the solution viscosity, which was adjusted by changing the glycerol content from 65% to 90% by volume in G/W mixtures. The kinetics of the GR of NO to Mp in viscous solutions was well represented by an exponential function with a time constant of ca. 11 ps. Although the kinetic traces of the GR of NO to Mp in solutions with three different viscosities (18, 81, and 252 cP) almost overlap, they show a slight difference early in the decay process. The kinetic traces were also described by the diffusion-controlled reaction theory with a Coulomb potential. Since the ligand is deligated in a neutral form, an ionic pair of NO(-) and Mp(+) may be produced before forming the Mp-NO bond by an electron transfer from Mp to NO as the deligated NO is sufficiently near to the Fe atom of Mp. The strong reactivity between NO and ferrous heme may arise from the Coulomb interaction between the reacting pair, which is consistent with the harpooning mechanism for NO binding to heme. PMID:26813691

  9. Time-resolved x-ray absorption spectroscopy: Watching atoms dance

    Energy Technology Data Exchange (ETDEWEB)

    Milne, Chris J; Pham, Van-Thai; Veen, Renske M van der; El Nahhas, Amal; Lima, Frederico; Vithanage, Dimali A; Chergui, Majed [Laboratoire de Spectroscopie Ultrarapide, Ecole Polytechnique Federale de Lausanne (Switzerland); Gawelda, Wojciech [Laser Processing Group, Instituto de Optica, CSIC (Spain); Johnson, Steven L; Beaud, Paul; Ingold, Gerhard; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Abela, Rafael [Swiss Light Source, Paul Scherrer Institut (Switzerland); Benfatto, Maurizio [Laboratori Nazionali di Frascati, INFN (Italy); Hauser, Andreas [Departement de Chimie Physique, Universite de Geneve (Switzerland); Bressler, Christian, E-mail: majed.chergui@epfl.c, E-mail: chris.milne@psi.c [European XFEL Project Team, Deutsches Elektronen Synchrotron (Germany)

    2009-11-15

    The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [Fe{sup II}(bpy){sub 3}]{sup 2+}, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 A. In addition an analysis technique using the reduced {chi}{sup 2} goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

  10. Time-resolved spectroscopy and fluorescence resonance energy transfer in the study of excimer laser damage of chromatin

    Science.gov (United States)

    Radu, L.; Mihailescu, I.; Radu, S.; Gazdaru, D.

    2007-09-01

    The analysis of chromatin damage produced by a 248 nm excimer laser radiation, for doses of 0.3-3 MJ/m 2 was carried out by time-resolved spectroscopy and fluorescence resonance energy transfer (FRET). The chromatin was extracted from a normal and a tumoral tissue of Wistar rats. The decrease with laser dose of the relative contribution of the excited state lifetimes of ethidium bromide (EtBr) bounded to chromatin constitutes an evidence of the reduction of chromatin deoxyribonucleic acid (DNA) double-strand structure. FRET was performed from dansyl chloride to acridine orange, both coupled to chromatin. The increase of the average distance between these ligands, under the action of laser radiation, reflects a loosening of the chromatin structure. The radiosensitivity of tumor tissue chromatin is higher than that of a normal tissue. The determination of the chromatin structure modification in an excimer laser field can be of interest in laser therapy.

  11. Probing dynamic crystal growth of compressed hydrogen using dynamic-DAC, time-resolved spectroscopy and highspeed micro-photography

    International Nuclear Information System (INIS)

    Solidification and crystal growth processes of hydrogen (H2) have been studied under dynamic compression using dynamic-DAC (dDAC) in conjunction with time resolved Raman spectroscopy and high-speed microphotography. Liquid H2 was compressed at a compression rate of 43 GPa/s across the liquid/solid phase boundary, causing a discontinuous vibron shift at the onset of solidification. The real time sample images, on the other hand, showed that H2 solidifies into a characteristic, grain boundary free crystal, formed initially from the outside (or the edge of liquid) then grew into the central area within 11 ms. Interestingly, the time scale associated with the glassy solid formation is in good agreement with that of the discontinuous Raman frequency shift. The rate of crystal growth was measured to be 0.3 cm/s.

  12. Ultrafast terahertz modulation characteristic of tungsten doped vanadium dioxide nanogranular film revealed by time-resolved terahertz spectroscopy

    International Nuclear Information System (INIS)

    The ultrafast terahertz (THz) modulation characteristic during photo-induced insulator-to-metal transition (IMT) of undoped and tungsten (W)-doped VO2 film was investigated at picoseconds time scale using time-resolved THz spectroscopy. W-doping slows down the photo-induced IMT dynamic processes (both the fast non-thermal process and the slow metallic phase propagation process) in VO2 film and also reduces the pump fluence threshold of photo-induced IMT in VO2 film. Along with the observed broadening of phase transition temperature window of IMT in W-doped VO2, we conclude that W-doping prevents metallic phase domains from percolation. By further extracting carrier properties from photo-induced THz conductivity at several phase transition times, we found that the electron-electron correlation during IMT is enhanced in W-doped VO2

  13. Homogeneous time-resolved G protein-coupled receptor-ligand binding assay based on fluorescence cross-correlation spectroscopy.

    Science.gov (United States)

    Antoine, Thomas; Ott, David; Ebell, Katharina; Hansen, Kerrin; Henry, Luc; Becker, Frank; Hannus, Stefan

    2016-06-01

    G protein-coupled receptors (GPCRs) mediate many important physiological functions and are considered as one of the most successful therapeutic target classes for a wide spectrum of diseases. Drug discovery projects generally benefit from a broad range of experimental approaches for screening compound libraries and for the characterization of binding modes of drug candidates. Owing to the difficulties in solubilizing and purifying GPCRs, assay formats have been so far mainly limited to cell-based functional assays and radioligand binding assays. In this study, we used fluorescence cross-correlation spectroscopy (FCCS) to analyze the interaction of detergent-solubilized receptors to various types of GPCR ligands: endogenous peptides, small molecules, and a large surrogate antagonist represented by a blocking monoclonal antibody. Our work demonstrates the suitability of the homogeneous and time-resolved FCCS assay format for a robust, high-throughput determination of receptor-ligand binding affinities and kinetic rate constants for various therapeutically relevant GPCRs. PMID:26954998

  14. Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

    Science.gov (United States)

    Ponseca, C. S., Jr.; Sundström, V.

    2016-03-01

    Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

  15. Wide-field time-resolved luminescence imaging and spectroscopy to decipher obliterated documents in forensic science

    Science.gov (United States)

    Suzuki, Mototsugu; Akiba, Norimitsu; Kurosawa, Kenji; Kuroki, Kenro; Akao, Yoshinori; Higashikawa, Yoshiyasu

    2016-01-01

    We applied a wide-field time-resolved luminescence (TRL) method with a pulsed laser and a gated intensified charge coupled device (ICCD) for deciphering obliterated documents for use in forensic science. The TRL method can nondestructively measure the dynamics of luminescence, including fluorescence and phosphorescence lifetimes, which prove to be useful parameters for image detection. First, we measured the TRL spectra of four brands of black porous-tip pen inks on paper to estimate their luminescence lifetimes. Next, we acquired the TRL images of 12 obliterated documents at various delay times and gate times of the ICCD. The obliterated contents were revealed in the TRL images because of the difference in the luminescence lifetimes of the inks. This method requires no pretreatment, is nondestructive, and has the advantage of wide-field imaging, which makes it is easy to control the gate timing. This demonstration proves that TRL imaging and spectroscopy are powerful tools for forensic document examination.

  16. Ultrafast terahertz modulation characteristic of tungsten doped vanadium dioxide nanogranular film revealed by time-resolved terahertz spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Yang [College of Materials Science and Engineering, Sichuan University, Chengdu, Sichuan 610065 (China); National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics & Terahertz Research Center, China Academy of Engineering Physics, Mianyang, Sichuan 621900 (China); Zhai, Zhao-Hui; Zhu, Li-Guo, E-mail: zhuliguo@tsinghua.org.cn, E-mail: huangwanxia@scu.edu.cn; Li, Jun; Peng, Qi-Xian; Li, Ze-Ren [National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics & Terahertz Research Center, China Academy of Engineering Physics, Mianyang, Sichuan 621900 (China); Shi, Qi-Wu; Huang, Wan-Xia, E-mail: zhuliguo@tsinghua.org.cn, E-mail: huangwanxia@scu.edu.cn; Yue, Fang; Hu, Yan-Yan [College of Materials Science and Engineering, Sichuan University, Chengdu, Sichuan 610065 (China)

    2015-07-20

    The ultrafast terahertz (THz) modulation characteristic during photo-induced insulator-to-metal transition (IMT) of undoped and tungsten (W)-doped VO{sub 2} film was investigated at picoseconds time scale using time-resolved THz spectroscopy. W-doping slows down the photo-induced IMT dynamic processes (both the fast non-thermal process and the slow metallic phase propagation process) in VO{sub 2} film and also reduces the pump fluence threshold of photo-induced IMT in VO{sub 2} film. Along with the observed broadening of phase transition temperature window of IMT in W-doped VO{sub 2}, we conclude that W-doping prevents metallic phase domains from percolation. By further extracting carrier properties from photo-induced THz conductivity at several phase transition times, we found that the electron-electron correlation during IMT is enhanced in W-doped VO{sub 2}.

  17. In situ time-resolved X-ray near-edge absorption spectroscopy of selenite reduction by siderite

    International Nuclear Information System (INIS)

    The reduction oxidation-reaction between aqueous selenite (SeO32-) and siderite (FeCO3(s)) was monitored by in situ, time-resolved X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K edge in a controlled electrochemical environment. Spectral evolutions showed that more than 60% of selenite was reduced at the siderite surface after 20 h of experiment, at which time the reaction was still incomplete. Fitting of XANES spectra by linear combination of reference spectra showed that selenite reaction with siderite is essentially a two-step process, selenite ions being immobilized on siderite surface prior to their reduction. A kinetic model of the reduction step is proposed, allowing to identify the specific contribution of surface reduction. These results have strong implications for the retention of selenite by corrosion products in nuclear waste repositories and in a larger extent for the fate of selenium in the environment. (authors)

  18. TIME-RESOLVED ULTRAVIOLET SPECTROSCOPY OF THE M-DWARF GJ 876 EXOPLANETARY SYSTEM

    Energy Technology Data Exchange (ETDEWEB)

    France, Kevin; Froning, Cynthia S. [Center for Astrophysics and Space Astronomy, University of Colorado, 389 UCB, Boulder, CO 80309 (United States); Linsky, Jeffrey L. [JILA, University of Colorado and NIST, 440 UCB, Boulder, CO 80309 (United States); Tian, Feng [Laboratory for Atmospheric and Space Physics, University of Colorado, Boulder, CO 80309 (United States); Roberge, Aki, E-mail: kevin.france@colorado.edu [Exoplanets and Stellar Astrophysics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States)

    2012-05-10

    Extrasolar planets orbiting M-stars may represent our best chance to discover habitable worlds in the coming decade. The ultraviolet spectrum incident upon both Earth-like and Jovian planets is critically important for proper modeling of their atmospheric heating and chemistry. In order to provide more realistic inputs for atmospheric models of planets orbiting low-mass stars, we present new near- and far-ultraviolet (NUV and FUV) spectroscopy of the M-dwarf exoplanet host GJ 876 (M4V). Using the COS and STIS spectrographs on board the Hubble Space Telescope, we have measured the 1150-3140 A spectrum of GJ 876. We have reconstructed the stellar H I Ly{alpha} emission line profile, and find that the integrated Ly{alpha} flux is roughly equal to the rest of the integrated flux (1150-1210 A + 1220-3140 A) in the entire ultraviolet bandpass (F(Ly{alpha})/F(FUV+NUV) Almost-Equal-To 0.7). This ratio is {approx}2500 Multiplication-Sign greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H{sub 2} (T(H{sub 2}) > 2000 K). We show the light curve of a chromospheric + transition region flare observed in several far-UV emission lines, with flare/quiescent flux ratios {>=}10. The strong FUV radiation field of an M-star (and specifically Ly{alpha}) is important for determining the abundance of O{sub 2}-and the formation of biomarkers-in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

  19. Ultrafast time-resolved absorption spectroscopy of geometric isomers of carotenoids

    International Nuclear Information System (INIS)

    The structures of a number of stereoisomers of carotenoids have been revealed in three-dimensional X-ray crystallographic investigations of pigment-protein complexes from photosynthetic organisms. Despite these structural elucidations, the reason for the presence of stereoisomers in these systems is not well understood. An important unresolved issue is whether the natural selection of geometric isomers of carotenoids in photosynthetic pigment-protein complexes is determined by the structure of the protein binding site or by the need for the organism to accomplish a specific physiological task. The association of cis isomers of a carotenoid with reaction centers and trans isomers of the same carotenoid with light-harvesting pigment-protein complexes has led to the hypothesis that the stereoisomers play distinctly different physiological roles. A systematic investigation of the photophysics and photochemistry of purified, stable geometric isomers of carotenoids is needed to understand if a relationship between stereochemistry and biological function exists. In this work we present a comparative study of the spectroscopy and excited state dynamics of cis and trans isomers of three different open-chain carotenoids in solution. The molecules are neurosporene (n = 9), spheroidene (n = 10), and spirilloxanthin (n = 13), where n is the number of conjugated π-electron double bonds. The spectroscopic experiments were carried out on geometric isomers of the carotenoids purified by high performance liquid chromatography (HPLC) and then frozen to 77 K to inhibit isomerization. The spectral data taken at 77 K provide a high resolution view of the spectroscopic differences between geometric isomers. The kinetic data reveal that the lifetime of the lowest excited singlet state of a cis-isomer is consistently shorter than that of its corresponding all-trans counterpart despite the fact that the excited state energy of the cis molecule is typically higher than that of the trans

  20. Application of near-infrared time-resolved spectroscopy to rat liver - a preliminary report for surgical application

    International Nuclear Information System (INIS)

    The applicability of near-infrared time-resolved spectroscopy to rat liver surgery was investigated. First, the technical reliability in determining the absorption coefficient (μa) and reduced scattering coefficient (μs) of the liver was checked. Next, boundary effects in determining μa and μs' of the rat liver were examined. Finally, changes in μa and μs' of rat liver with ischaemia were directly measured by TRS. Our TRS system showed that the μa value held a linear correlation with the ink concentration in a lipid emulsion until μa reached 1.2 cm-1, while the μs' was fairly independent. The μa values of blood-free rat liver and blood-containing rat liver at 780 nm were observed to be 0.43cm-1 and 0.67cm-1 by using the matching method, indicating that TRS is reliable in determining μa and μs' of the liver. Possible errors in μa and μs' determination due to the boundary effects of the rat liver were as small as 7%, when the μa value was as high as observed for the liver. The oxygen saturation of haemoglobin (SO2) was changed from 64.9% to 8.0%, and the haemoglobin content (THB) from 189.1 μM to 131.6 μM by ischaemia. μs' dynamically changed in the range 7.06cm-1 to 11.36cm-1. We conclude that time-resolved measurement is applicable in the high-μa region observed in the liver, and can give quantitative estimations of SO2 and THB in the liver. (author)

  1. Utility and constraint on the use of pump-probe photoelectron spectroscopy for detecting time-resolved surface photovoltage

    International Nuclear Information System (INIS)

    Highlights: ► The pump-probe PES method for detecting time-resolved surface photovoltage (SPV) is analyzed. ► The simulation for the trip of the electron from the sample to the analyzer revealed its utility and constraint. ► The basic time-resolution is determined by the pump-spot radius and the electron energy. ► The lifetime of the SPV that is shorter than the time-resolution can be correctly monitored. -- Abstract: Utility and constraints on using the pump-probe photoelectron spectroscopy for detecting the time-resolved surface photovoltage on the semiconductor surface are discussed by solving the equation of motion for the electron from the sample to the analyzer. The escape time, which is defined as the time for the electron to achieve the 99% of the photovoltage, determines the basic temporal resolution. It can be derived from a simple formula with the pump beam radius and the initial kinetic energy of the electron and lies in a range of nano seconds with a usual experimental condition so far. However, an analysis revealed that a time constant for the decay in the SPV can be correctly measured with the decay in the kinetic-energy shift as a function of the pump-probe time difference even for a much shorter time constant than the escape time. Meanwhile, the value of the kinetic-energy shift does not agree with the true SPV. The relation between the true SPV and the observed kinetic-energy shift is estimated.

  2. Utility and constraint on the use of pump-probe photoelectron spectroscopy for detecting time-resolved surface photovoltage

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Shin-ichiro, E-mail: stanaka@sanken.osaka-u.ac.jp [The Institute of the Industrial and Scientific Research, Osaka University, 567-0047 Mihogaoka, Ibaraki, Osaka (Japan)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer The pump-probe PES method for detecting time-resolved surface photovoltage (SPV) is analyzed. Black-Right-Pointing-Pointer The simulation for the trip of the electron from the sample to the analyzer revealed its utility and constraint. Black-Right-Pointing-Pointer The basic time-resolution is determined by the pump-spot radius and the electron energy. Black-Right-Pointing-Pointer The lifetime of the SPV that is shorter than the time-resolution can be correctly monitored. -- Abstract: Utility and constraints on using the pump-probe photoelectron spectroscopy for detecting the time-resolved surface photovoltage on the semiconductor surface are discussed by solving the equation of motion for the electron from the sample to the analyzer. The escape time, which is defined as the time for the electron to achieve the 99% of the photovoltage, determines the basic temporal resolution. It can be derived from a simple formula with the pump beam radius and the initial kinetic energy of the electron and lies in a range of nano seconds with a usual experimental condition so far. However, an analysis revealed that a time constant for the decay in the SPV can be correctly measured with the decay in the kinetic-energy shift as a function of the pump-probe time difference even for a much shorter time constant than the escape time. Meanwhile, the value of the kinetic-energy shift does not agree with the true SPV. The relation between the true SPV and the observed kinetic-energy shift is estimated.

  3. Development of a dual-modal tissue diagnostic system combining time-resolved fluorescence spectroscopy and ultrasonic backscatter microscopy.

    Science.gov (United States)

    Sun, Yang; Park, Jesung; Stephens, Douglas N; Jo, Javier A; Sun, Lei; Cannata, Jonathan M; Saroufeem, Ramez M G; Shung, K Kirk; Marcu, Laura

    2009-06-01

    We report a tissue diagnostic system which combines two complementary techniques of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) and ultrasonic backscatter microscopy (UBM). TR-LIFS evaluates the biochemical composition of tissue, while UBM provides tissue microanatomy and enables localization of the region of diagnostic interest. The TR-LIFS component consists of an optical fiber-based time-domain apparatus including a spectrometer, gated multichannel plate photomultiplier, and fast digitizer. It records the fluorescence with high sensitivity (nM concentration range) and time resolution as low as 300 ps. The UBM system consists of a transducer, pulser, receiving circuit, and positioning stage. The transducer used here is 45 MHz, unfocused, with axial and lateral resolutions 38 and 200 microm. Validation of the hybrid system and ultrasonic and spectroscopic data coregistration were conducted both in vitro (tissue phantom) and ex vivo (atherosclerotic tissue specimens of human aorta). Standard histopathological analysis of tissue samples was used to validate the UBM-TRLIFS data. Current results have demonstrated that spatially correlated UBM and TR-LIFS data provide complementary characterization of both morphology (necrotic core and calcium deposits) and biochemistry (collagen, elastin, and lipid features) of the atherosclerotic plaques at the same location. Thus, a combination of fluorescence spectroscopy with ultrasound imaging would allow for better identification of features associated with tissue pathologies. Current design and performance of the hybrid system suggests potential applications in clinical diagnosis of atherosclerotic plaque. PMID:19566223

  4. Characterization of post mortem arterial tissue using time-resolved photoacoustic spectroscopy at 436, 461 and 532 nm

    International Nuclear Information System (INIS)

    Time-resolved photoacoustic spectroscopy has been used to characterize post mortem arterial tissue for the purpose of discriminating between normal and atheromatous areas of tissue. Ultrasonic thermoelastic waves were generated in post mortem human aorta by the absorption of nanosecond laser pulses at 436, 461 and 532 nm produced by a frequency doubled Q-switched d:YAG laser in conjunction with a gas filled Raman cell. A PVDF membrane zydrophone was used to detect the thermoelastic waves. At 436 nm, differences in the photoacoustic signatures of normal tissue and atherorma were found to be highly variable. At 461 nm, there was a clear and reproducible difference between the photoacoustic response of atheroma and normal tissue as a result of increased optical attenuation in atheroma. At 532 nm, the generation of subsurface thermoelastic waves provided a means of determining the structure and thickness of the tissue sample. It is suggested that pulsed photoacoustic spectroscopy at 461 and 532 nm may find application in characterizing arterial tissue in situ by providing information about both the composition and thickness of the vessel wall. (author)

  5. Probing the hydrogen-bond network of water via time-resolved soft x-ray spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils; Wen, Haidan; Nordlund, Dennis; Szilagyi, Erzsi; Daranciang, Dan; Miller, Timothy A.; Nilsson, Anders; Schoenlein, Robert W.; Lindenberg, Aaron M.

    2009-04-24

    We report time-resolved studies of hydrogen bonding in liquid H2O, in response to direct excitation of the O-H stretch mode at 3 mu m, probed via soft x-ray absorption spectroscopy at the oxygen K-edge. This approach employs a newly developed nanofluidic cell for transient soft x-ray spectroscopy in liquid phase. Distinct changes in the near-edge spectral region (XANES) are observed, and are indicative of a transient temperature rise of 10K following transient laser excitation and rapid thermalization of vibrational energy. The rapid heating occurs at constant volume and the associated increase in internal pressure, estimated to be 8MPa, is manifest by distinct spectral changes that differ from those induced by temperature alone. We conclude that the near-edge spectral shape of the oxygen K-edge is a sensitive probe of internal pressure, opening new possibilities for testing the validity of water models and providing new insight into the nature of hydrogen bonding in water.

  6. Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.; Ratajczak, E.

    The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...

  7. Time-Resolved Spectroscopy and Near Infrared Imaging for Prostate Cancer Detection: Receptor-targeted and Native Biomarker

    Science.gov (United States)

    Pu, Yang

    Optical spectroscopy and imaging using near-infrared (NIR) light provides powerful tools for non-invasive detection of cancer in tissue. Optical techniques are capable of quantitative reconstructions maps of tissue absorption and scattering properties, thus can map in vivo the differences in the content of certain marker chromophores and/or fluorophores in normal and cancerous tissues (for example: water, tryptophan, collagen and NADH contents). Potential clinical applications of optical spectroscopy and imaging include functional tumor detection and photothermal therapeutics. Optical spectroscopy and imaging apply contrasts from intrinsic tissue chromophores such as water, collagen and NADH, and extrinsic optical contrast agents such as Indocyanine Green (ICG) to distinguish disease tissue from the normal one. Fluorescence spectroscopy and imaging also gives high sensitivity and specificity for biomedical diagnosis. Recent developments on specific-targeting fluorophores such as small receptor-targeted dye-peptide conjugate contrast agent offer high contrast between normal and cancerous tissues hence provide promising future for early tumour detection. This thesis focus on a study to distinguish the cancerous prostate tissue from the normal prostate tissues with enhancement of specific receptor-targeted prostate cancer contrast agents using optical spectroscopy and imaging techniques. The scattering and absorption coefficients, and anisotropy factor of cancerous and normal prostate tissues were investigated first as the basis for the biomedical diagnostic and optical imaging. Understanding the receptors over-expressed prostate cancer cells and molecular target mechanism of ligand, two small ICG-derivative dye-peptides, namely Cypate-Bombesin Peptide Analogue Conjugate (Cybesin) and Cypate-Octreotate Peptide Conjugate (Cytate), were applied to study their clinical potential for human prostate cancer detection. In this work, the steady-state and time-resolved

  8. Single-shot Raman spectroscopy and time-resolved reflectivity of a shocked TATB-based explosive

    Science.gov (United States)

    Hebert, Philippe; Saint-Amans, Charles; Doucet, Michel; de Resseguier, Thibaut

    2015-06-01

    Single-shot Raman spectroscopy experiments under shockwave loading were performed in order to get information on the initiation mechanisms that can lead to sustained detonation of a TATB-based explosive. Shocks up to 30 GPa were generated using a two-stage laser-driven flyer plate generator. The samples were confined by an optical window and shock pressure was maintained for at least 30 ns. Photon Doppler Velocimetry measurements were performed at the explosive/window interface to determine the shock pressure profile. Raman spectra were recorded as a function of shock pressure and the shifts of the principal modes were compared to static high-pressure measurements performed in a diamond anvil cell. Our shock data indicate the role of temperature effects on the H-bonding network present in TATB. Our Raman spectra also show a progressive extinction of the signal which disappears around 9 GPa. High-speed photography images reveal a simultaneous progressive darkening of the sample surface up to total opacity at 9 GPa. Time-resolved reflectivity measurements under shock compression seem to indicate that this opacity is due to a broadening of the absorption spectrum over the entire visible region.

  9. Sub-100ps single photoelectron time resolution of a strip silicon photomultiplier for time-resolved optical spectroscopy

    Science.gov (United States)

    Wang, Shenyuan; Liu, Rongdan; Liang, Kun; Yang, Ru; Han, Dejun

    2015-10-01

    SiPM with epitaxial quenching resistors developed at NDL (Novel Device Laboratory, Beijing) could alleviate the conflict between large dynamic range and high photon detection efficiency (PDE). It can be used as low light level detector in various applications with excellent single photoelectron time resolution (SPTR) and photon counting capacity. SPTR is mainly determined by the intrinsic structure parameters of the SiPM. However, it is also limited to measurement setup, electronics readout and the ultra-small signal of single photoelectron level. In this work, we designed and fabricated a 1 mm × 1 mm strip SiPM array for possible applications in time-resolved optical spectroscopy. The SiPM array consists of sixteen 50 μm × 1 mm strip SiPM elements. Each element contains five hundred 6.5 μm × 6.5 μm micro avalanche photodiode (APD) cells with 10μm pitch. The strip SiPM demonstrated SPTR of 68 ps (FWHM), peak PDE of 17% around 450 nm and high photon number resolving and photon counting capability.

  10. Time-resolved X-Ray Absorption Spectroscopy of a Cobalt-Based Hydrogen Evolution System for Artificial Photosynthesis

    Science.gov (United States)

    Moonshiram, Dooshaye; Gimbert, Carolina; Lehmann, Carl; Southworth, Stephen; Llobet, Antoni; Argonne National Laboratory Team; Institut Català d'Investigació Química Collaboration

    2015-03-01

    Production of cost-effective hydrogen gas through solar power is an important challenge of the Department of Energy among other global industry initiatives. In natural photosynthesis, the oxygen evolving complex(OEC) can carry out four-electron water splitting to hydrogen with an efficiency of around 60%. Although, much progress has been carried out in determining mechanistic pathways of the OEC, biomimetic approaches have not duplicated Nature's efficiency in function. Over the past years, we have witnessed progress in developments of light harvesting modules, so called chromophore/catalytic assemblies. In spite of reportedly high catalytic activity of these systems, quantum yields of hydrogen production are below 40 % when using monochromatic light. Proper understanding of kinetics and bond making/breaking steps has to be achieved to improve efficiency of hydrogen evolution systems. This project shows the timing implementation of ultrafast X-ray absorption spectroscopy to visualize in ``real time'' the photo-induced kinetics accompanying a sequence of redox reactions in a cobalt-based molecular photocatalytic system. Formation of a Co(I) species followed by a Co(III) hydride species all the way towards hydrogen evolution is shown through time-resolved XANES.

  11. NO kinetics in pulsed low-pressure plasmas studied by time-resolved quantum cascade laser absorption spectroscopy

    International Nuclear Information System (INIS)

    Time-resolved quantum cascade laser absorption spectroscopy at 1897 cm-1 (5.27 μm) has been applied to study the NO(X) kinetics on the micro- and millisecond time scale in pulsed low-pressure N2/NO dc discharges. Experiments have been performed under flowing and static gas conditions to infer the gas temperature increase and the consequences for the NO line strength. A relatively small increase of ∼20 K is observed during the early plasma phase of a few milliseconds. After some 10 ms gas temperatures up to 500 K can be deduced. The experimental data for the NO mixing ratio were compared with the results from a recently developed time-dependent model for pulsed N2-O2 plasmas which are well in accord. The early plasma pulse is determined by vibrational heating of N2 while the excitation of NO(X) by N2 metastables is almost completely balanced. Efficient NO depletion occurs after several milliseconds by N atom impact.

  12. NO kinetics in pulsed low-pressure plasmas studied by time-resolved quantum cascade laser absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Welzel, S; Roepcke, J [INP-Greifswald, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Guaitella, O; Lazzaroni, C; Rousseau, A [LPP, Ecole Polytechnique, UPMC, Universite Paris Sud-11, CNRS, 91128 Palaiseau Cedex (France); Pintassilgo, C D, E-mail: welzel.s@freenet.de [Instituto de Plasmas e Fusao Nuclear-Laboratorio Associado, Instituto Superior Tecnico, 1049-001 Lisboa (Portugal)

    2011-02-15

    Time-resolved quantum cascade laser absorption spectroscopy at 1897 cm{sup -1} (5.27 {mu}m) has been applied to study the NO(X) kinetics on the micro- and millisecond time scale in pulsed low-pressure N{sub 2}/NO dc discharges. Experiments have been performed under flowing and static gas conditions to infer the gas temperature increase and the consequences for the NO line strength. A relatively small increase of {approx}20 K is observed during the early plasma phase of a few milliseconds. After some 10 ms gas temperatures up to 500 K can be deduced. The experimental data for the NO mixing ratio were compared with the results from a recently developed time-dependent model for pulsed N{sub 2}-O{sub 2} plasmas which are well in accord. The early plasma pulse is determined by vibrational heating of N{sub 2} while the excitation of NO(X) by N{sub 2} metastables is almost completely balanced. Efficient NO depletion occurs after several milliseconds by N atom impact.

  13. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Guorong [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Schalk, Oliver [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); Sekikawa, Taro [Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Worth, Graham A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario K1N 6N5 (Canada)

    2016-01-07

    The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A{sub 2}(πσ{sup ∗}) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B{sub 1}(π3p{sub y}) Rydberg state, followed by prompt internal conversion to the A{sub 2}(πσ{sup ∗}) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A{sub 2}(πσ{sup ∗}) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A{sub 2}(πσ{sup ∗}) state, facilitating wavepacket motion around the potential barrier in the N–CH{sub 3} dissociation coordinate.

  14. A multi-analytical investigation of semi-conductor pigments with time-resolved spectroscopy and imaging

    Science.gov (United States)

    Nevin, A.; Cesaratto, A.; D'Andrea, C.; Valentini, Gianluca; Comelli, D.

    2013-05-01

    We present the non-invasive study of historical and modern Zn- and Cd-based pigments with time-resolved fluorescence spectroscopy, fluorescence multispectral imaging and fluorescence lifetime imaging (FLIM). Zinc oxide and Zinc sulphide are semiconductors which have been used as white pigments in paintings, and the luminescence of these pigments from trapped states is strongly dependent on the presence of impurities and crystal defects. Cadmium sulphoselenide pigments vary in hue from yellow to deep red based on their composition, and are another class of semiconductor pigments which emit both in the visible and the near infrared. The Fluorescence lifetime of historical and modern pigments has been measured using both an Optical Multichannel Analyser (OMA) coupled with a Nd:YAG nslaser, and a streak camera coupled with a ps-laser for spectrally-resolved fluorescence lifetime measurements. For Znbased pigments we have also employed Fluorescence Lifetime Imaging (FLIM) for the measurement of luminescence. A case study of FLIM applied to the analysis of the painting by Vincent Van Gogh on paper - "Les Bretonnes et le pardon de Pont-Aven" (1888) is presented. Through the integration of complementary, portable and non-invasive spectroscopic techniques, new insights into the optical properties of Zn- and Cd-based pigments have been gained which will inform future analysis of late 19th] and early 20th C. paintings.

  15. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    International Nuclear Information System (INIS)

    The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A2(πσ∗) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B1(π3py) Rydberg state, followed by prompt internal conversion to the A2(πσ∗) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A2(πσ∗) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A2(πσ∗) state, facilitating wavepacket motion around the potential barrier in the N–CH3 dissociation coordinate

  16. Time-resolved optical spectroscopy on Er-doped fluorozirconate-based glasses for efficient up-conversion

    Energy Technology Data Exchange (ETDEWEB)

    Skrzypczak, Ulrich; Miclea, Manuela [Centre for Innovation Competence SiLi-nano, Martin Luther University of Halle-Wittenberg, Halle (Saale) (Germany); Johnson, Jacqueline A. [Department of Materials Science and Engineering, University of Tennessee Space Institute, Tullahoma, TN (United States); Schweizer, Stefan [Centre for Innovation Competence SiLi-nano, Martin Luther University of Halle-Wittenberg, Halle (Saale) (Germany); Fraunhofer Center for Silicon Photovoltaics, Halle (Saale) (Germany)

    2010-07-01

    Fluorozirconate(FZ)-based glasses have shown their potential as hosts for rare-earth (RE) ions such as Er, in these glasses REs show emissions that would be quenched in other glasses. Such material systems are of practical interest for photon up-conversion. For photovoltaic applications, the efficiency of bifacial solar cells could be vastly improved by an up-converting back layer. Up-conversion is the sequential absorption of two or more low-energy infrared photons by a RE ion followed by subsequent emission of a visible photon. This process is dependent on the intermediate level lifetime of the RE ion, which is determined by the phonon energies of the host material. Low phonon energy glasses like FZ glasses are thus desirable hosts. The lifetimes of the energy levels involved in the up-conversion process are investigated by time-resolved spectroscopy. Short laser pulses at different wavelengths are used for excitation; the emissions are detected via time-correlated photon counting. The radiative and non-radiative decay processes in Er-doped FZ glasses are analyzed and discussed.

  17. ''Live'' Prussian blue fading by time-resolved X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gervais, Claire [Smithsonian Institution Museum Conservation Institute, Suitland, MD (United States); Bern University of the Arts, Bern (Switzerland); Languille, Marie-Angelique [Synchrotron SOLEIL, IPANEMA, USR 3461 CNRS/MCC, Gif-sur-Yvette (France); Reguer, Solenn [Synchrotron SOLEIL, DiffAbs beamline, Gif-sur-Yvette (France); Gillet, Martine [Museum national d' histoire naturelle, Centre de Recherche sur la Conservation des Collections, Paris (France); Vicenzi, Edward P. [Smithsonian Institution Museum Conservation Institute, Suitland, MD (United States); Chagnot, Sebastien; Baudelet, Francois [Synchrotron SOLEIL, ODE beamline, Gif-sur-Yvette (France); Bertrand, Loic [Synchrotron SOLEIL, IPANEMA, USR 3461 CNRS/MCC, Gif-sur-Yvette (France); Synchrotron SOLEIL, Gif-sur-Yvette (France)

    2013-04-15

    Prussian blue (PB) is an artists' pigment that has been frequently used in many artworks but poses several problems of conservation because of its fading under light and anoxia treatment. PB fading is due to the reduction of iron(III) into iron(II) and depends a lot on the object investigated. Due to the complexity of the structure, the precise physico-chemical mechanisms behind the redox process remain obscure. In this paper, we present a procedure to investigate light- and anoxia-induced fading of PB-paper samples by means of time resolved X-ray absorption spectroscopy performed at the Fe K-edge. A system composed of a visible light source and a flux-controlled environmental cell allowed light, gas and humidity to be modified in situ. The synchrotron X-ray beam was evidenced to induce a reduction of PB and to play a major role in the kinetics. The analysis of the PB fading kinetics of a sample submitted to various gas and light environments showed that both synchrotron beam and anoxia were influencing PB reduction in a correlated way. In comparison, light was found to play a minor role. Finally, we have demonstrated that the type of paper substrate could influence significantly the kinetics of reduction. Several hypotheses to explain the correlation between PB reduction mechanism and substrate are presented. (orig.)

  18. HELIOS—A laboratory based on high-order harmonic generation of extreme ultraviolet photons for time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Plogmaker, S., E-mail: Stefan.Plogmaker@physics.uu.se, E-mail: Joachim.Terschluesen@physics.uu.se, E-mail: Johan.Soderstrom@physics.uu.se; Terschlüsen, J. A., E-mail: Stefan.Plogmaker@physics.uu.se, E-mail: Joachim.Terschluesen@physics.uu.se, E-mail: Johan.Soderstrom@physics.uu.se; Krebs, N.; Svanqvist, M.; Forsberg, J.; Cappel, U. B.; Rubensson, J.-E.; Siegbahn, H.; Söderström, J., E-mail: Stefan.Plogmaker@physics.uu.se, E-mail: Joachim.Terschluesen@physics.uu.se, E-mail: Johan.Soderstrom@physics.uu.se [Department of Physics and Astronomy, Molecular and Condensed Matter Physics, Uppsala University, P.O. Box 516, 75120 Uppsala (Sweden)

    2015-12-15

    In this paper, we present the HELIOS (High Energy Laser Induced Overtone Source) laboratory, an in-house high-order harmonic generation facility which generates extreme ultraviolet (XUV) photon pulses in the range of 15-70 eV with monochromatized XUV pulse lengths below 35 fs. HELIOS is a source for time-resolved pump-probe/two-color spectroscopy in the sub-50 fs range, which can be operated at 5 kHz or 10 kHz. An optical parametric amplifier is available for pump-probe experiments with wavelengths ranging from 240 nm to 20 000 nm. The produced XUV radiation is monochromatized by a grating in the so-called off-plane mount. Together with overall design parameters, first monochromatized spectra are shown with an intensity of 2 ⋅ 10{sup 10} photons/s (at 5 kHz) in the 29th harmonic, after the monochromator. The XUV pulse duration is measured to be <25 fs after monochromatization.

  19. Time-resolved optical spectroscopy on Er-doped fluorozirconate-based glasses for efficient up-conversion

    International Nuclear Information System (INIS)

    Fluorozirconate(FZ)-based glasses have shown their potential as hosts for rare-earth (RE) ions such as Er, in these glasses REs show emissions that would be quenched in other glasses. Such material systems are of practical interest for photon up-conversion. For photovoltaic applications, the efficiency of bifacial solar cells could be vastly improved by an up-converting back layer. Up-conversion is the sequential absorption of two or more low-energy infrared photons by a RE ion followed by subsequent emission of a visible photon. This process is dependent on the intermediate level lifetime of the RE ion, which is determined by the phonon energies of the host material. Low phonon energy glasses like FZ glasses are thus desirable hosts. The lifetimes of the energy levels involved in the up-conversion process are investigated by time-resolved spectroscopy. Short laser pulses at different wavelengths are used for excitation; the emissions are detected via time-correlated photon counting. The radiative and non-radiative decay processes in Er-doped FZ glasses are analyzed and discussed.

  20. Time-resolved terahertz spectroscopy of electrically conductive metal-organic frameworks doped with redox active species

    Science.gov (United States)

    Alberding, Brian G.; Heilweil, Edwin J.

    2015-09-01

    Metal-Organic Frameworks (MOFs) are three-dimensional coordination polymers that are well known for large pore surface area and their ability to adsorb molecules from both the gaseous and solution phases. In general, MOFs are electrically insulating, but promising opportunities for tuning the electronic structure exist because MOFs possess synthetic versatility; the metal and organic ligand subunits can be exchanged or dopant molecules can be introduced into the pore space. Two such MOFs with demonstrated electrical conductivity are Cu3(1,3,5-benzenetricarboxylate)2, a.k.a HKUST-1, and Cu[Ni(pyrazine-2,3-dithiolate)2]. Herein, these two MOFs have been infiltrated with the redox active species 7,7,8,8-tetracyanoquinodimethane (TCNQ) and iodine under solution phase conditions and shown to produce redox products within the MOF pore space. Vibrational bands assignable to TCNQ anion and triiodide anion have been observed in the Mid-IR and Terahertz ranges using FTIR Spectroscopy. The MOF samples have been further investigated by Time-Resolved Terehertz Spectroscopy (TRTS). Using this technique, the charge mobility, separation, and recombination dynamics have been followed on the picosecond time scale following photoexcitation with visible radiation. The preliminary results show that the MOF samples have small inherent photoconductivity with charge separation lifetimes on the order of a few picoseconds. In the case of HKUST-1, the MOF can also be supported by a TiO2 film and initial results show that charge injection into the TiO2 layer occurs with a comparable efficiency to the dye sensitizer N3, [cis-Bis(isothiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)], and therefore this MOF has potential as a new light absorbing and charge conducting material in photovoltaic devices.

  1. Nonlinear spectroscopy in the near-field: time resolved spectroscopy and subwavelength resolution non-invasive imaging

    Science.gov (United States)

    Namboodiri, Mahesh; Khan, Tahirzeb; Karki, Khadga; Kazemi, Mehdi Mohammad; Bom, Sidhant; Flachenecker, Günter; Namboodiri, Vinu; Materny, Arnulf

    2014-04-01

    The combination of near-field microscopy along with nonlinear optical spectroscopic techniques is presented here. The scanning near-field imaging technique can be integrated with nonlinear spectroscopic techniques to improve spatial and axial resolution of the images. Additionally, ultrafast dynamics can be probed down to nano-scale dimension. The review shows some examples for this combination, which resulted in an exciton map and vibrational contrast images with sub-wavelength resolution. Results of two-color femtosecond time-resolved pump-probe experiments using scanning near-field optical microscopy (SNOM) on thin films of the organic semiconductor 3,4,9,10 Perylenetetracarboxylic dianhydride (PTCDA) are presented. While nonlinear Raman techniques have been used to obtain highly resolved images in combination with near-field microscopy, the use of femtosecond laser pulses in electronic resonance still constitutes a big challenge. Here, we present our first results on coherent anti-Stokes Raman scattering (fs-CARS) with femtosecond laser pulses detected in the near-field using SNOM. We demonstrate that highly spatially resolved images can be obtained from poly(3-hexylthiophene) (P3HT) nano-structures where the fs-CARS process was in resonance with the P3HT absorption and with characteristic P3HT vibrational modes without destruction of the samples. Sub-diffraction limited lateral resolution is achieved. Especially the height resolution clearly surpasses that obtained with standard microCARS. These results will be the basis for future investigations of mode-selective dynamics in the near-field.

  2. Optimization of Supercontinuum Sources for Ultra-Broadband T-CARS Spectroscopy

    International Nuclear Information System (INIS)

    For a typical photonic crystal fiber with two zero-dispersion wavelengths, we theoretically demonstrate a new way to generate supercontinuum using an input pulse of 30 fs duration and 10 kW peak power for providing a compact and cost effective light source to the ultra-broadband time-resolved coherent anti-Stokes Raman scattering spectroscopy. (fundamental areas of phenomenology(including applications))

  3. Time resolved spectroscopy of SGR J1550–5418 bursts detected with Fermi/gamma-ray burst monitor

    International Nuclear Information System (INIS)

    We report on a time-resolved spectroscopy of the 63 brightest bursts of SGR J1550–5418, detected with the Fermi/Gamma-ray Burst Monitor during its 2008-2009 intense bursting episode. We performed spectral analysis down to 4 ms timescales to characterize the spectral evolution of the bursts. Using a Comptonized model, we find that the peak energy, E peak, anti-correlates with flux, while the low-energy photon index remains constant at ∼ – 0.8 up to a flux limit F ≈ 10–5 erg s–1 cm–2. Above this flux value, the E peak–flux correlation changes sign, and the index positively correlates with the flux reaching ∼1 at the highest fluxes. Using a two blackbody model, we find that the areas and fluxes of the two emitting regions correlate positively. Further, we study here for the first time the evolution of the temperatures and areas as a function of flux. We find that the area–kT relation follows the lines of constant luminosity at the lowest fluxes, R 2∝kT –4, with a break at the higher fluxes (F > 10–5.5 erg s–1 cm–2). The area of the high-kT component increases with the flux while its temperature decreases, which we interpret as being due to an adiabatic cooling process. The area of the low-kT component, on the other hand, appears to saturate at the highest fluxes, toward R max ≈ 30 km. Assuming that crust quakes are responsible for soft gamma repeater (SGR) bursts and considering R max as the maximum radius of the emitting photon-pair plasma fireball, we relate this saturation radius to a minimum excitation radius of the magnetosphere, and we put a lower limit on the internal magnetic field of SGR J1550–5418, B int ≳ 4.5 × 1015 G.

  4. Time Resolved Spectroscopy of SGR J1550-5418 Bursts Detected with Fermi/Gamma-Ray Burst Monitor

    Science.gov (United States)

    Younes, G.; Kouveliotou, C.; van der Horst, A. J.; Baring, M. G.; Granot, J.; Watts, A. L.; Bhat, P. N.; Collazzi, A.; Gehrels, N.; Gorgone, N.; Göğüş, E.; Gruber, D.; Grunblatt, S.; Huppenkothen, D.; Kaneko, Y.; von Kienlin, A.; van der Klis, M.; Lin, L.; Mcenery, J.; van Putten, T.; Wijers, R. A. M. J.

    2014-04-01

    We report on a time-resolved spectroscopy of the 63 brightest bursts of SGR J1550-5418, detected with the Fermi/Gamma-ray Burst Monitor during its 2008-2009 intense bursting episode. We performed spectral analysis down to 4 ms timescales to characterize the spectral evolution of the bursts. Using a Comptonized model, we find that the peak energy, E peak, anti-correlates with flux, while the low-energy photon index remains constant at ~ - 0.8 up to a flux limit F ≈ 10-5 erg s-1 cm-2. Above this flux value, the E peak-flux correlation changes sign, and the index positively correlates with the flux reaching ~1 at the highest fluxes. Using a two blackbody model, we find that the areas and fluxes of the two emitting regions correlate positively. Further, we study here for the first time the evolution of the temperatures and areas as a function of flux. We find that the area-kT relation follows the lines of constant luminosity at the lowest fluxes, R 2vpropkT -4, with a break at the higher fluxes (F > 10-5.5 erg s-1 cm-2). The area of the high-kT component increases with the flux while its temperature decreases, which we interpret as being due to an adiabatic cooling process. The area of the low-kT component, on the other hand, appears to saturate at the highest fluxes, toward R max ≈ 30 km. Assuming that crust quakes are responsible for soft gamma repeater (SGR) bursts and considering R max as the maximum radius of the emitting photon-pair plasma fireball, we relate this saturation radius to a minimum excitation radius of the magnetosphere, and we put a lower limit on the internal magnetic field of SGR J1550-5418, B int >~ 4.5 × 1015 G.

  5. Electronic Excited State and Vibrational Dynamics of Water Solution of Cytosine Observed by Time-resolved Transient Absorption Spectroscopy with Sub-10fs Deep Ultraviolet Laser Pules

    Directory of Open Access Journals (Sweden)

    Kobayashi Takayoshi.

    2013-03-01

    Full Text Available Time-resolved transient absorption spectroscopy for water solution of cytosine with sub-10fs deep ultraviolet laser pulse is reported. Ultrafast electronic excited state dynamics and coherent molecular vibrational dynamics are simultaneously observed and their relaxation mechanisms are discussed.

  6. Insights into the charge carrier terahertz mobility in polyfluorenes from large-scale atomistic simulations and time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Vukmirović, N.; Ponseca, C.S.; Němec, Hynek; Yartsev, A.; Sundström, V.

    2012-01-01

    Roč. 116, č. 37 (2012), s. 19665-1972. ISSN 1932-7447 Institutional research plan: CEZ:AV0Z10100520 Keywords : charge carrier mobility * time-resolved terahertz spectroscopy * multiscale atomistic calculations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.814, year: 2012

  7. Electron-hole recombination on ZnO(0001) single-crystal surface studied by time-resolved soft X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yukawa, R.; Yamamoto, S.; Ogawa, M.; Yamamoto, Sh.; Fujikawa, K.; Hobara, R.; Matsuda, I., E-mail: imatsuda@issp.u-tokyo.ac.jp [Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan); Ozawa, K. [Department of Chemistry and Materials Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551 (Japan); Emori, M.; Sakama, H. [Department of Physics, Sophia University, Chiyoda-ku, Tokyo 102-8554 (Japan); Kitagawa, S.; Daimon, H. [Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192 (Japan)

    2014-10-13

    Time-resolved soft X-ray photoelectron spectroscopy (PES) experiments were performed with time scales from picoseconds to nanoseconds to trace relaxation of surface photovoltage on the ZnO(0001) single crystal surface in real time. The band diagram of the surface has been obtained numerically using PES data, showing a depletion layer which extends to 1 μm. Temporal evolution of the photovoltage effect is well explained by a recombination process of a thermionic model, giving the photoexcited carrier lifetime of about 1 ps at the surface under the flat band condition. This lifetime agrees with a temporal range reported by the previous time-resolved optical experiments.

  8. Broadband single-molecule excitation spectroscopy

    Science.gov (United States)

    Piatkowski, Lukasz; Gellings, Esther; van Hulst, Niek F.

    2016-01-01

    Over the past 25 years, single-molecule spectroscopy has developed into a widely used tool in multiple disciplines of science. The diversity of routinely recorded emission spectra does underpin the strength of the single-molecule approach in resolving the heterogeneity and dynamics, otherwise hidden in the ensemble. In early cryogenic studies single molecules were identified by their distinct excitation spectra, yet measuring excitation spectra at room temperature remains challenging. Here we present a broadband Fourier approach that allows rapid recording of excitation spectra of individual molecules under ambient conditions and that is robust against blinking and bleaching. Applying the method we show that the excitation spectra of individual molecules exhibit an extreme distribution of solvatochromic shifts and distinct spectral shapes. Importantly, we demonstrate that the sensitivity and speed of the broadband technique is comparable to that of emission spectroscopy putting both techniques side-by-side in single-molecule spectroscopy.

  9. Complexation of polyacrylates by Ca2+ ions. Time-resolved studies using attenuated total reflectance Fourier transform infrared dialysis spectroscopy.

    Science.gov (United States)

    Fantinel, Fabiana; Rieger, Jens; Molnar, Ferenc; Hübler, Patrick

    2004-03-30

    The attenuated total reflectance Fourier transform infrared dialysis technique is introduced for the time-resolved investigation of the binding processes of Ca2+ to polyacrylates dissolved in water. We observed transient formation of intermediates in water with various types of coordination of the carboxylate group to Ca2+ throughout the complexation steps. Time-resolved changes in the spectra were analyzed with principal component analysis, from which the spectral species were obtained as well as their formation kinetics. We propose a model for the mechanisms of Ca2+ coordination to polyacrylates. The polymer chain length plays an important role in Ca2+ binding. PMID:15835120

  10. Time resolved spectroscopy of SGR J1550–5418 bursts detected with Fermi/gamma-ray burst monitor

    Energy Technology Data Exchange (ETDEWEB)

    Younes, G. [Universities Space Research Association, 6767 Old Madison Pike, Suite 450, Huntsville, AL 35806 (United States); Kouveliotou, C.; Collazzi, A. [Astrophysics Office, ZP 12, NASA-Marshall Space Flight Center, Huntsville, AL 35812 (United States); Van der Horst, A. J.; Watts, A. L.; Huppenkothen, D.; Van der Klis, M.; Van Putten, T. [Astronomical Institute " Anton Pannekoek," University of Amsterdam, Postbus 94249, 1090 GE Amsterdam (Netherlands); Baring, M. G. [Department of Physics and Astronomy, Rice University, MS-108, P.O. Box 1892, Houston, TX 77251 (United States); Granot, J. [Department of Natural Sciences, The Open University of Israel, 1 University Road, P.O. Box 808, Raánana 43537 (Israel); Bhat, P. N.; Gorgone, N. [University of Alabama in Huntsville CSPAR, 320 Sparkman Drive, Huntsville, AL 35805 (United States); Gehrels, N.; Mcenery, J. [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Göğüş, E.; Kaneko, Y.; Lin, L. [Sabancı University, Orhanlı-Tuzla, İstanbul 34956 (Turkey); Gruber, D.; Von Kienlin, A. [Max Planck Institute for Extraterrestrial Physics, Giessenbachstrasse, Postfach 1312, D-85748 Garching (Germany); Grunblatt, S. [University of Hawaii at Manoa, 2500 Campus Road, Honolulu, HI 96822 (United States); and others

    2014-04-10

    We report on a time-resolved spectroscopy of the 63 brightest bursts of SGR J1550–5418, detected with the Fermi/Gamma-ray Burst Monitor during its 2008-2009 intense bursting episode. We performed spectral analysis down to 4 ms timescales to characterize the spectral evolution of the bursts. Using a Comptonized model, we find that the peak energy, E {sub peak}, anti-correlates with flux, while the low-energy photon index remains constant at ∼ – 0.8 up to a flux limit F ≈ 10{sup –5} erg s{sup –1} cm{sup –2}. Above this flux value, the E {sub peak}–flux correlation changes sign, and the index positively correlates with the flux reaching ∼1 at the highest fluxes. Using a two blackbody model, we find that the areas and fluxes of the two emitting regions correlate positively. Further, we study here for the first time the evolution of the temperatures and areas as a function of flux. We find that the area–kT relation follows the lines of constant luminosity at the lowest fluxes, R {sup 2}∝kT {sup –4}, with a break at the higher fluxes (F > 10{sup –5.5} erg s{sup –1} cm{sup –2}). The area of the high-kT component increases with the flux while its temperature decreases, which we interpret as being due to an adiabatic cooling process. The area of the low-kT component, on the other hand, appears to saturate at the highest fluxes, toward R {sub max} ≈ 30 km. Assuming that crust quakes are responsible for soft gamma repeater (SGR) bursts and considering R {sub max} as the maximum radius of the emitting photon-pair plasma fireball, we relate this saturation radius to a minimum excitation radius of the magnetosphere, and we put a lower limit on the internal magnetic field of SGR J1550–5418, B {sub int} ≳ 4.5 × 10{sup 15} G.

  11. Guest–Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates

    DEFF Research Database (Denmark)

    Haldrup, Martin Kristoffer; Vanko, G.; Gawelda, W.;

    2012-01-01

    We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)3]2+ in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate...

  12. Time-resolved FTIR spectroscopy for monitoring protein dynamics exemplified by functional studies of Ras protein bound to a lipid bilayer

    International Nuclear Information System (INIS)

    Graphical abstract: The first time resolved FTIR investigation of a GTPase reaction of a protein anchored at a single lipid bilayer. Display Omitted Highlights: ► FTIR difference spectroscopy monitors protein dynamics with atomic detail. ► ATR–FTIR allows the measurement of a monolayer sample. ► Membrane proteins can be investigated near physiological conditions. ► The hydrolysis reaction of Ras was investigated in this condition for the first time. - Abstract: Time-resolved Fourier transform infrared (FTIR) difference spectroscopy is a valuable tool for monitoring the dynamics of protein reactions and interactions. Absorbance changes can be monitored with time resolutions down to nanoseconds and followed for time periods that range over nine orders of magnitude. Membrane proteins bound to solid supported lipid bilayers can be investigated in near physiological conditions with the attenuated total reflection (ATR) technique. Here, we review the basics of time-resolved FTIR with a focus on Ras, a GTPase that is mutated in 25% of human tumors. We show the first time-resolved measurements of membrane anchored Ras and observed the switching between its activated and its inactivated state. We compared those measurements with measurements of the truncated Ras in solution. We found that both the kinetics and the functional groups involved were very similar. This suggested that the membrane did not have a major influence on the hydrolysis reaction.

  13. Distribution of protons from a plasma focus in velocity-time space by time-resolved Thomson spectroscopy

    International Nuclear Information System (INIS)

    A time-resolving Thomson spectrometer has been used to analyze the protons produced by a plasma focus. The authors use a compact Thomson spectrometer and modulate the electric field--a time-resolving Thomson spectrometer. The resulting spectrograms have patterns of particle tracks that are oscillatory about the θ-b axis (i.e., the line of zero electric deflection). The zero-crossing, intersections of the trace with the θ-b axis, provide information about the relative arrival time of particles at the spectrometer (chi=iota). As with the conventional Thomson spectrometer, the magnetic deflection provides the particle velocity. This velocity is plotted versus particle arrival time. This plot is then transformed to velocity versus particle production time at the plasma focus (chi=0). The authors have adjusted the experimental parameters to improve time resolution from about one nanosecond to sub-nanosecond. This allows a coarse plot of particle number distribution in velocity-time space. Their experimental set-up is designed to produce a 123 MHz modulation in the electric field using a transmitter at that frequency, instead of the 27 MHz used previously. Also a shortened drift region provides increased particle intensity on the spectrograms. The particle detector is CR-39 plastic, which is etched to reveal particle tracks that are visible under an optical microscope. The resulting time-resolved Thomson spectrograms have more zero-crossings than before, thus providing improved time resolution

  14. NI-49SMART SUCKER: NEXT GENERATION SMART SURGICAL TOOL FOR INTRAOPERATIVE BRAIN TUMOR RESECTION USING TIME RESOLVED LASER INDUCED FLUORESCENCE SPECTROSCOPY

    OpenAIRE

    Kittle, David S.; Butte, Pramod V.; Vasefi, Fartash; Patil, Chirag G.; Black, Keith

    2014-01-01

    Primary brain tumors are highly lethal tumors where surgical resection is the primary treatment of choice. It has been shown that survival rate is directly related to the extent of tumor resection. In order to aid the surgeon in achieving near-complete resection, novel technologies are required. Time-resolved laser induced fluorescence spectroscopy (TRLIFS) promises to be one such technology, where the tissue is excited using an ultra-short laser and the corresponding fluorescence intensity d...

  15. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    International Nuclear Information System (INIS)

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  16. Photoinduced phenoxyl radical formation from ligno- p-cresol as studied by steady-state and time-resolved EPR spectroscopy

    Science.gov (United States)

    Tero-Kubota, Shozo; Tachikawa, Takashi; Ito, Fuyuki; Matsui, Mikio; Konishi, Kazuyori

    2003-11-01

    The phenoxyl radical formation mechanism from the UV-photolysis of ligno- p-cresol in organic solvents has been investigated by steady-state and time-resolved EPR spectroscopy. It is suggested that the phenoxyl radical is generated from the o-methoxy phenol moiety in the main chain of the polymer through the dissociative photoionization by the biphotonic process from the excited triplet states.

  17. Time-resolved resonance Raman spectroscopy of 1,3,5-hexatrienes in the lowest excited triplet state. The potential energy surface in T1

    OpenAIRE

    Wilbrandt, R; Langkilde, F.W.; Brouwer, A.M.; Negri, F; Orlandi, G.

    1990-01-01

    Time-resolved resonance Raman spectroscopy is applied to the study of the T1 state of 1,3,5-hexatriene and deuteriated and methylated derivatives in solution. The technique is described briefly. The experimentally obtained resonance Raman spectra are discussed in the light of theoretical Quantum Chemical Force Field calculations. Implications for the potential energy surface of the T1 state are discussed.

  18. Dynamics of Propane in Silica Mesopores Formed upon Propylene Hydrogenation over Pt Nanoparticles by Time-Resolved FT-IR Spectroscopy

    OpenAIRE

    Waslylenko, Walter; Frei, Heinz

    2008-01-01

    Propylene hydrogenation over Pt nanoparticles supported on mesoporous silica type SBA-15 was monitored by time-resolved FT-IR spectroscopy at 23 ms resolution using short propylene gas pulses that joined a continuous flow of hydrogen in N2 (1 atm total pressure). Experiments were conducted in the temperature range 323-413 K. Propane was formed within 100 milliseconds or faster. The CH stretching region revealed distinct bands for propane molecules emerging inside the nanoscale channels o...

  19. Comparison of beetroot extracts originating from several sites using time-resolved laser-induced fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Beetroot (Beta vulgaris) juice contains a large number of fluorophores which can fluoresce. There is a growing interest in beetroot extracts analysis. In contrast, there is only limited information about beetroot obtained without sample preparation and/or extraction of components from the sample. In this work, we continue our previous study (Rabasović et al 2009 Acta Phys. Pol. A 116 570-2), analyzing and comparing beetroot extracts from several sites, using the time-resolved laser-induced fluorescence technique to measure the fluorescence of samples at different excitation wavelengths (340-470 nm) and for different sample dilutions.

  20. Comparison of beetroot extracts originating from several sites using time-resolved laser-induced fluorescence spectroscopy

    Science.gov (United States)

    Rabasović, M. S.; Šević, D.; Terzić, M.; Marinković, B. P.

    2012-05-01

    Beetroot (Beta vulgaris) juice contains a large number of fluorophores which can fluoresce. There is a growing interest in beetroot extracts analysis. In contrast, there is only limited information about beetroot obtained without sample preparation and/or extraction of components from the sample. In this work, we continue our previous study (Rabasović et al 2009 Acta Phys. Pol. A 116 570-2), analyzing and comparing beetroot extracts from several sites, using the time-resolved laser-induced fluorescence technique to measure the fluorescence of samples at different excitation wavelengths (340-470 nm) and for different sample dilutions.

  1. Multichannel, time-resolved picosecond laser ultrasound imaging and spectroscopy with custom complementary metal-oxide-semiconductor detector

    International Nuclear Information System (INIS)

    This paper presents a multichannel, time-resolved picosecond laser ultrasound system that uses a custom complementary metal-oxide-semiconductor linear array detector. This novel sensor allows parallel phase-sensitive detection of very low contrast modulated signals with performance in each channel comparable to that of a discrete photodiode and a lock-in amplifier. Application of the instrument is demonstrated by parallelizing spatial measurements to produce two-dimensional thickness maps on a layered sample, and spectroscopic parallelization is demonstrated by presenting the measured Brillouin oscillations from a gallium arsenide wafer. This paper demonstrates the significant advantages of our approach to pump probe systems, especially picosecond ultrasonics.

  2. Multi-channel lock-in amplifier assisted femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy with efficient rejection of superfluorescence background

    Science.gov (United States)

    Mao, Pengcheng; Wang, Zhuan; Dang, Wei; Weng, Yuxiang

    2015-12-01

    Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300-1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10-5M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process.

  3. Fluorescence-suppressed time-resolved Raman spectroscopy of pharmaceuticals using complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector.

    Science.gov (United States)

    Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J; Yliperttula, Marjo

    2016-01-01

    In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is possible to overcome the strong fluorescence background that usually interferes with the much weaker Raman spectra. Second, using the high photon energy excitation light source, we are able to generate a stronger Raman signal compared to traditional instruments. In addition, observations in the time domain can be performed, thus enabling new capabilities in the field of Raman and fluorescence spectroscopy. With this system, we demonstrate for the first time the possibility of recording fluorescence-suppressed Raman spectra of solid, amorphous and crystalline, and non-photoluminescent and photoluminescent drugs such as caffeine, ranitidine hydrochloride, and indomethacin (amorphous and crystalline forms). The raw data acquired by utilizing only the picosecond pulsed laser and a CMOS SPAD detector could be used for identifying the compounds directly without any data processing. Moreover, to validate the accuracy of this time-resolved technique, we present density functional theory (DFT) calculations for a widely used gastric acid inhibitor, ranitidine hydrochloride. The obtained time-resolved Raman peaks were identified based on the calculations and existing literature. Raman spectra using non-time-resolved setups with continuous-wave 785- and 532-nm excitation lasers were used as reference data. Overall, this demonstration of time-resolved Raman and fluorescence measurements with a CMOS SPAD detector shows promise in diverse areas, including fundamental chemical research, the

  4. Multi-channel lock-in amplifier assisted femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy with efficient rejection of superfluorescence background

    International Nuclear Information System (INIS)

    Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300–1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10−5M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process

  5. Multi-channel lock-in amplifier assisted femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy with efficient rejection of superfluorescence background

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Pengcheng; Wang, Zhuan; Dang, Wei; Weng, Yuxiang, E-mail: yxweng@aphy.iphy.ac.cn [Key Laboratory of Soft Matter Physics, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2015-12-15

    Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300–1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10{sup −5}M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process.

  6. Probing organometallic reactions by time-resolved infrared spectroscopy in solution and in the solid state using quantum cascade lasers.

    Science.gov (United States)

    Calladine, James A; Horvath, Raphael; Davies, Andrew J; Wriglesworth, Alisdair; Sun, Xue-Zhong; George, Michael W

    2015-05-01

    The photochemistry and photophysics of metal carbonyl compounds (W(CO)6, Cp*Rh(CO)2 (Cp* = η(5)-C5Me5), and fac-[Re(CO)3(4,4'-bpy)2Br] [bpy = bipyridine]) have been examined on the nanosecond timescale using a time-resolved infrared spectrometer with an external cavity quantum cascade laser (QCL) as the infrared source. We show the photochemistry of W(CO)6 in alkane solution is easily monitored, and very sensitive measurements are possible with this approach, meaning it can monitor small transients with absorbance changes less than 10(-6) ΔOD. The C-H activation of Cp*Rh(CO)(C6H12) to form Cp*Rh(CO)(C6H11)H occurs within the first few tens of nanoseconds following photolysis, and we demonstrate that kinetics obtained following deconvolution are in excellent agreement with those measured using an ultrafast laser-based spectrometer. We also show that the high flux and tunability of QCLs makes them suited for solid-state and time-resolved measurements. PMID:25811673

  7. Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

    Science.gov (United States)

    Hebert, Philippe; Saint-Amans, Charles

    2013-06-01

    A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

  8. Employing time-resolved terahertz spectroscopy to analyze carrier dynamics in thin-film Cu2ZnSn(S,Se)4 absorber layers

    International Nuclear Information System (INIS)

    We report the application of time-resolved terahertz spectroscopy (TRTS) to measure photoexcited carrier lifetimes and mobility, and to determine recombination mechanisms in Cu2ZnSn(S,Se)4 (CZTSSe) thin films fabricated from nanocrystal inks. Ultrafast time resolution permits tracking the evolution of carrier density to determine recombination rates and mechanisms. The carrier generation profile was manipulated by varying the photoexcitation wavelength and fluence to distinguish between surface, Shockley-Read-Hall (SRH), radiative, and Auger recombination mechanisms and determine rate constants. Surface and SRH recombination are the dominant mechanisms for the air/CZTSSe/SiO2/Si film stack. Diffusion to, and then recombination at, the air-CZTSSe interface occurred on the order of 100 picoseconds, while SRH recombination lifetimes were 1–2 nanoseconds. TRTS measurements can provide information that is complementary to conventional time-resolved photoluminescence measurements and can direct the design of efficient thin film photovoltaics.

  9. Photocarrier dynamics in undoped and Na-doped Cu2ZnSnS4 single crystals revealed by ultrafast time-resolved terahertz spectroscopy

    Science.gov (United States)

    Quang Phuong, Le; Okano, Makoto; Yamashita, Genki; Nagai, Masaya; Ashida, Masaaki; Nagaoka, Akira; Yoshino, Kenji; Kanemitsu, Yoshihiko

    2015-06-01

    We investigated the effects of sodium doping on the photocarrier dynamics in Cu2ZnSnS4 (CZTS) single crystals using optical pump-THz probe transient reflectivity (THz-TR) and time-resolved photoluminescence (PL) spectroscopy. The THz-TR and PL decay dynamics are influenced by sodium doping, and their sodium-induced changes are consistent with each other. These time-resolved measurements revealed that the lifetime of photocarriers increases with sodium doping. This result indicates that a part of defects is suppressed by doping sodium into CZTS and implies that sodium doping improves the charge transport properties of CZTS, leading to an improvement in the performance of CZTS-based solar cells.

  10. Time-resolvedspectroscopy measurements of hot-electron equilibration dynamics in thin-foil solid targets: Collisional and collective effects

    International Nuclear Information System (INIS)

    Time-resolvedspectroscopy measurements from high-intensity laser interactions with thin-foil solid targets are reviewed. Thin Cu foils were irradiated with 1- to 10-J, 1-ps pulses at focused intensities from 1018 to 1019 W/cm2. The experimental data show Kα-emission pulse widths from 3 to 6 ps, increasing with laser intensity. The time-resolved Kα-emission data are compared to a hot-electron transport and Kα-production model that includes collisional electron-energy coupling, resistive heating, and electromagnetic field effects. The experimental data show good agreement with the model when a reduced ponderomotive scaling is used to describe the initial mean hot-electron energy over the relevant intensity range

  11. Investigation of verbal and visual working memory by multi-channel time-resolved functional near-infrared spectroscopy

    Science.gov (United States)

    Contini, D.; Caffini, M.; Re, R.; Zucchelli, L.; Spinelli, L.; Basso Moro, S.; Bisconti, S.; Ferrari, M.; Quaresima, V.; Cutini, S.; Torricelli, A.

    2013-03-01

    Working memory (WM) is fundamental for a number of cognitive processes, such as comprehension, reasoning and learning. WM allows the short-term maintenance and manipulation of the information selected by attentional processes. The goal of this study was to examine by time-resolved fNIRS neural correlates of the verbal and visual WM during forward and backward digit span (DF and DB, respectively) tasks, and symbol span (SS) task. A neural dissociation was hypothesised between the maintenance and manipulation processes. In particular, a dorsolateral/ventrolateral prefrontal cortex (DLPFC/VLPFC) recruitment was expected during the DB task, whilst a lateralised involvement of Brodmann Area (BA) 10 was expected during the execution of the DF task. Thirteen subjects were monitored by a multi-channel, dual-wavelength (690 and 829 nm) time-resolved fNIRS system during 3 minutes long DF and DB tasks and 4 minutes long SS task. The participants' mean memory span was calculated for each task: DF: 6.46+/-1.05 digits; DB: 5.62+/-1.26 digits; SS: 4.69+/-1.32 symbols. No correlation was found between the span level and the heart rate data (measured by pulse oximeter). As expected, DB elicited a broad activated area, in the bilateral VLPFC and the right DLPFC, whereas a more localised activation was observed over the right hemisphere during either DF (BA 10) or SS (BA 10 and 44). The robust involvement of the DLPFC during DB, compared to DF, is compatible with previous findings and with the key role of the central executive subserving in manipulating processes.

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

    Science.gov (United States)

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

    1995-01-01

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

  13. Time-resolved spectroscopy of complex scintillators Al2BeO4, Be2SiO4 and Al2Be3Si6O18

    International Nuclear Information System (INIS)

    The present work is devoted to investigations of the luminescence properties of aluminum-, beryllium- and silicon-containing complex wide gap oxides in energy range 2.5-32 eV at temperature 10-300 K using time-resolved VUV-spectroscopy and ionluminescence methods. It has been shown that all studied crystals possess intrinsic luminescence in the UV-region of spectrum. Phenomenon of electron excitations multiplication has been found in excitation spectra of intrinsic luminescence. The difference and typical features of photoluminescence and ionluminescence (luminescence excited by accelerated particle beam) are discussed

  14. Time-resolved tunable diode laser absorption spectroscopy of excited argon and ground-state titanium atoms in pulsed magnetron discharges

    Czech Academy of Sciences Publication Activity Database

    Sushkov, V.; Do, H.T.; Čada, Martin; Hubička, Zdeněk; Hippler, R.

    2013-01-01

    Roč. 22, č. 1 (2013), 1-10. ISSN 0963-0252 R&D Projects: GA ČR(CZ) GAP205/11/0386; GA ČR GAP108/12/2104 Institutional research plan: CEZ:AV0Z10100522 Keywords : absorption spectroscopy * diode laser * magnetron * argon metastable * HiPIMS * titanium * time-resolved Subject RIV: BH - Optics, Masers, Lasers Impact factor: 3.056, year: 2013 http://iopscience.iop.org/0963-0252/22/1/015002/

  15. Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)_(3)(dppz)(py)]^(+)–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy

    OpenAIRE

    Olmon, Eric D.; Sontz, Pamela A.; Blanco-Rodríguez, Ana María; Towrie, Michael; Clark, Ian P; Vlček, Antonín; Barton, Jacqueline K.

    2011-01-01

    The complex [Re(CO)_(3)(dppz)(py′-OR)]+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; py′-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re–DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the ex...

  16. Time resolved study of the emission enhancement mechanisms in orthogonal double-pulse laser-induced breakdown spectroscopy

    Science.gov (United States)

    Sanginés, R.; Sobral, H.

    2013-10-01

    The evolution of laser induced ablation plume on aluminum targets has been investigated in orthogonal pre-ablation double pulse scheme at atmospheric pressure from the earliest stages of plasma evolution. Time-resolved emission spectra from neutrals, singly- and doubly-ionized species obtained with the double pulse experiment have been compared with those from the single pulse configuration. Signal-to-noise enhancement reaches values of up to 15 depending on the analyzed species; and the lower the charge state the later its maximum signal-to-noise ratio is reached. Ablation plume dynamics was monitored from 10 ns after the plasma onset via shadowgraphy and fast-photography with narrow interference filters to follow the evolution of individual species. Results show that ionic species from the target are located at the plasma core while nitrogen from the background air is found at the plume peripheral. Initially both configurations exhibit similar ablation plume sizes and their expansions were successfully fitted with the strong explosion model for the first 500 ns. At later times a good agreement was obtained by using the drag model, which predicts that the plume expansion eventually stops due to interaction with the background gas particles. The emission enhancement measured in the double pulse scheme is discussed in terms of the models describing the plume dynamics.

  17. Ultrafast nuclear dynamics in halomethanes studied with time-resolved Coulomb explosion imaging and channel-selective Fourier spectroscopy

    Science.gov (United States)

    Malakar, Y.; Kaderiya, B.; Pearson, W. L.; Ziaee, F.; Kanaka Raju, P.; Zohrabi, M.; Jensen, K.; Rajput, J.; Ben-Itzhak, I.; Rolles, D.; Rudenko, A.

    2016-05-01

    Halomethanes have recently attracted considerable attention since they often serve as prototype systems for laser-controlled chemistry (e.g., selective bond breaking or concerted elimination reactions), and are important molecules in atmospheric chemistry. Here we combine a femtosecond laser pump-probe setup with coincident 3D ion momentum imaging apparatus to study strong-field induced nuclear dynamics in methane and several of its halogenated derivatives (CH3 I, CH2 I2, CH2 ICl). We apply a time-resolved Coulomb explosion imaging technique to map the nuclear motion on both, bound and continuum potential surfaces, disentangle different fragmentation pathways and, for halogenated molecules, observe clear signatures of vibrational wave packets in neutral or ionized states. Channel-selective and kinetic-energy resolved Fourier analysis of these data allows for unique identification of different electronic states and vibrational modes responsible for a particular structure. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. DOE. K. R. P. and W. L. P. supported by NSF Award No. IIA-143049. K.J. supported by the NSF-REU Grant No. PHYS-1461251.

  18. Characterization of the ionization degree evolution of the PF-400J plasma sheath by means of time resolved optical spectroscopy

    Science.gov (United States)

    Avaria, G.; Cuadrado, O.; Moreno, J.; Pavez, C.; Soto, L.

    2016-05-01

    Spectral measurements in the visible range of the plasma sheath ionization degree evolution on the plasma focus device PF-400J are presented. The measurements were done with temporal and spatial resolution in a plasma focus device of low stored energy: PF-400J (176-539 J, 880 nF, 20-35 kV, quarter period ∼ 300ns) [1]. An ICCD was attached to a 0.5 m focal length visible spectrometer, which enabled the acquisition of time resolved spectrum with 20 ns integration time throughout the whole current pulse evolution. The spatial resolution was attained using a set of lenses which allowed the focusing of a small volume of the plasma sheath in different positions of the inter-electrode space. Discharges were carried out in mixtures of Hydrogen with gases in different proportions: 5% Neon, 5% Krypton and 2% Nitrogen. Discharges using Neon as an impurity showed no ionization of the gas, just a very low intensity emission of Ne I at times much larger than the maximum current. Nitrogen, on the other hand, showed a high ionization reaching N V (N 4+) at the end of the axial phase, with a distinctive evolution of the ionization degree as the plasma sheath moved towards the end of the electrodes. A mixed result was found when using Krypton, since the ionization degree only reached levels around Kr II/III, even though it has an ionization potential lower than Neon.

  19. Studies on U(VI)-salicylate Charge Transfer Complex Formation by Using Time-resolved Laser Fluorescence Spectroscopy

    International Nuclear Information System (INIS)

    Organic ligands, such as humic and fulvic acids, play important roles in dissolution and migration of actinide radionuclide species. They can form stable actinide complexes in the presence of inorganic ions like hydroxides and carbonates. Therefore, the structural mimics of such ligands containing carboxylic and phenolic functional groups have been targets of studies to understand their chemical behaviors migrating actinides under geological groundwater conditions. Among many carboxylic ligands salycylate (SA) is useful to examine the role of phenolic groups on humic substances. Salicylate ion can form ligand-to-metal chargetransfer (LMCT) complexes with various metal ions. It has been shown that the fluorescence of SA is suppressed in the presence of Cu(II) or Eu(III) at pH 4 by forming ground state complexes. While uranyl ions also can form complex with SA, the dominant species at pH 4-7 region is known to be an 1:1 complex. However, the chemical structures reported on this 1:1 species are different among [UO2SA]0, [UO2(OH)SAH]0 and [UO2(OH)SA]-. For α- hydroxycarboxylates cyclic chelate structures were suggested where both carboxylate and phenolate groups simultaneously bind to uranyl ion. In the present study we investigate aqueous U(VI)- SA complex systems by using UV-Vis absorbance measurement and highly sensitive time-resolved laserinduced fluorescence spectroscopic (TRLFS) technique. The U(VI)-SA complex shows two characteristic charge-transfer (CT) bands at higher pH (> 4), which we found useful to examine the complexation equilibrium. Further, the TRLFS method is used to study the fluorescence (FL) quenching of U(VI) species, particularly for hydroxouranyl species at pH 4.5 of which FL is significantly suppressed as SA concentration elevates in aqueous solution. Fluorescence quenching mechanism in conjunction with the formation of U(VI)-SA CT complex is discussed

  20. Mapping of calf muscle oxygenation and haemoglobin content during dynamic plantar flexion exercise by multi-channel time-resolved near-infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Torricelli, Alessandro [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy); Quaresima, Valentina [Department of Biomedical Sciences and Technologies, University of L' Aquila, I-67100 L' Aquila (Italy); Pifferi, Antonio [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy); Biscotti, Giovanni [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy); Spinelli, Lorenzo [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy); Taroni, Paola [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy); Ferrari, Marco [Department of Biomedical Sciences and Technologies, University of L' Aquila, I-67100 L' Aquila (Italy); Cubeddu, Rinaldo [INFM-Dipartimento di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milan (Italy)

    2004-03-07

    A compact and fast multi-channel time-resolved near-infrared spectroscopy system for tissue oximetry was developed. It employs semiconductor laser and fibre optics for delivery of optical signals. Photons are collected by eight 1 mm fibres and detected by a multianode photomultiplier. A time-correlated single photon counting board is used for the parallel acquisition of time-resolved reflectance curves. Estimate of the reduced scattering coefficient is achieved by fitting with a standard model of diffusion theory, while the modified Lambert-Beer law is used to assess the absorption coefficient. In vivo measurements were performed on five healthy volunteers to monitor spatial changes in calf muscle (medial and lateral gastrocnemius; MG, LG) oxygen saturation (SmO{sub 2}) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO{sub 2} was 73.0 {+-} 0.9 and 70.5 {+-} 1.7% in MG and LG, respectively (P = 0.045). At the end of the exercise, SmO{sub 2} decreased (69.1 {+-} 1.8 and 63.8 {+-} 2.1% in MG and LG, respectively; P < 0.01). The LG desaturation was greater than the MG desaturation (P < 0.02). These results strengthen the role of time-resolved near-infrared spectroscopy as a powerful tool for investigating the spatial and temporal features of muscle SmO{sub 2} and tHb.

  1. A Q-switched Ho:YAG laser assisted nanosecond time-resolved T-jump transient mid-IR absorbance spectroscopy with high sensitivity.

    Science.gov (United States)

    Li, Deyong; Li, Yunliang; Li, Hao; Wu, Xianyou; Yu, Qingxu; Weng, Yuxiang

    2015-05-01

    Knowledge of dynamical structure of protein is an important clue to understand its biological function in vivo. Temperature-jump (T-jump) time-resolved transient mid-IR absorbance spectroscopy is a powerful tool in elucidating the protein dynamical structures and the folding/unfolding kinetics of proteins in solution. A home-built setup of T-jump time-resolved transient mid-IR absorbance spectroscopy with high sensitivity is developed, which is composed of a Q-switched Cr, Tm, Ho:YAG laser with an output wavelength at 2.09 μm as the T-jump heating source, and a continuous working CO laser tunable from 1580 to 1980 cm(-1) as the IR probe. The results demonstrate that this system has a sensitivity of 1 × 10(-4) ΔOD for a single wavelength detection, and 2 × 10(-4) ΔOD for spectral detection in amide I' region, as well as a temporal resolution of 20 ns. Moreover, the data quality coming from the CO laser is comparable to the one using the commercial quantum cascade laser. PMID:26026512

  2. A Q-switched Ho:YAG laser assisted nanosecond time-resolved T-jump transient mid-IR absorbance spectroscopy with high sensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Li, Deyong; Li, Yunliang; Li, Hao; Weng, Yuxiang, E-mail: yxweng@iphy.ac.cn [Key Laboratory of Soft Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Wu, Xianyou [Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031 (China); Yu, Qingxu [School of Physics and Optoelectronic Technology, Dalian University of Technology, No. 2, Linggong Road, Dalian 116023 (China)

    2015-05-15

    Knowledge of dynamical structure of protein is an important clue to understand its biological function in vivo. Temperature-jump (T-jump) time-resolved transient mid-IR absorbance spectroscopy is a powerful tool in elucidating the protein dynamical structures and the folding/unfolding kinetics of proteins in solution. A home-built setup of T-jump time-resolved transient mid-IR absorbance spectroscopy with high sensitivity is developed, which is composed of a Q-switched Cr, Tm, Ho:YAG laser with an output wavelength at 2.09 μm as the T-jump heating source, and a continuous working CO laser tunable from 1580 to 1980 cm{sup −1} as the IR probe. The results demonstrate that this system has a sensitivity of 1 × 10{sup −4} ΔOD for a single wavelength detection, and 2 × 10{sup −4} ΔOD for spectral detection in amide I′ region, as well as a temporal resolution of 20 ns. Moreover, the data quality coming from the CO laser is comparable to the one using the commercial quantum cascade laser.

  3. Broadband Dielectric Spectroscopy on Human Blood

    CERN Document Server

    Wolf, M; Lunkenheimer, P; Loidl, A

    2011-01-01

    Dielectric spectra of human blood reveal a rich variety of dynamic processes. Achieving a better characterization and understanding of these processes not only is of academic interest but also of high relevance for medical applications as, e.g., the determination of absorption rates of electromagnetic radiation by the human body. The dielectric properties of human blood are studied using broadband dielectric spectroscopy, systematically investigating the dependence on temperature and hematocrit value. By covering a frequency range from 1 Hz to 40 GHz, information on all the typical dispersion regions of biological matter is obtained. We find no evidence for a low-frequency relaxation (alpha-relaxation) caused, e.g., by counterion diffusion effects as reported for some types of biological matter. The analysis of a strong Maxwell-Wagner relaxation arising from the polarization of the cell membranes in the 1-100 MHz region (beta-relaxation) allows for the test of model predictions and the determination of variou...

  4. Time -resolved FTIR emission spectroscopy of Au in the 1800-4000 cm-1 region: New Rydberg transitions

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Chernov, V. E.; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr

    Madrid: The Spanish Royal Society of Physics, 2010. -. [European Conference on Atoms Molecules and Photons /10./. 04.08.2010-09.08.2010, Salamanca] R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : FTIR spectroscopy * Au Subject RIV: CF - Physical ; Theoretical Chemistry

  5. Time-resolved fluorescence correlation spectroscopy combined with lifetime tuning: New perspectives in supported phospholipid bilayers´ research

    Czech Academy of Sciences Publication Activity Database

    Benda, Aleš; Fagulová, Veronika; Deineka, Alexander; Enderlein, J.; Hof, Martin

    Berlin : Max Delbrück Center for Molecular Medicine, 2006 - (Cardoso, M.). s. 46 [International Symposium Optical Analysis of Biomolecular Machines. 13.07.2006-16.07.2006, Berlin] Institutional research plan: CEZ:AV0Z40400503 Keywords : fluorescence-correlation spectroscopy * phospholipid bilayers research * physical chemistry Subject RIV: CF - Physical ; Theoretical Chemistry

  6. Spatial density profile of electrons near the LaAlO3/SrTiO3 heterointerface revealed by time-resolved photoluminescence spectroscopy

    International Nuclear Information System (INIS)

    The depth profile of the electron density near the LaAlO3/SrTiO3 heterointerface has been studied by means of time-resolved photoluminescence (PL) spectroscopy. A broad blue PL band is observed at 2.9 eV, originating from the two-carrier radiative recombination of interface-induced electrons and photoexcited holes. The PL lifetime of LaAlO3/SrTiO3 heterointerface is dominated by the three-carrier Auger recombination of electrons and holes and is sensitive to electron density. We tuned the probing depth by changing the excitation photon energy and evaluated the carrier-density profile using the relation between the carrier density and the PL lifetime. Our non-contact probe method based on PL spectroscopy indicates that the carriers are confined within several nanometers in depth near the LaAlO3/SrTiO3 heterostructures

  7. TCSPC Upgrate of a confocal FCS microscope and first useful applications of time-resolved fluorescence correlation spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Benda, Aleš; Kapusta, P.; Fagulová, Veronika; Hof, Martin

    Santarém : Sociedade Portuguesa de Química , 2005 - (Tavares, E.). s. 73 ISBN 972-99080-7-9. [MAF 9. International Conference on Methods and Applications of Fluorescence. Spectroscopy, Imaging and Probes /9./. 4.9. - 7.9. 2005, Lisbon] R&D Projects: GA ČR GA203/05/2308 Institutional research plan: CEZ:AV0Z40400503 Keywords : TCSPC * TTTR * FCS microscope Subject RIV: CF - Physical ; Theoretical Chemistry

  8. Time-Resolved Fourier Transform Emission Spectroscopy of He/CH4 in a Positive Column Discharge

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Kubelík, Petr; Ferus, Martin

    2012-01-01

    Roč. 116, č. 12 (2012), s. 3137-3147. ISSN 1089-5639 R&D Projects: GA AV ČR IAA400400705; GA AV ČR IAAX00100903; GA ČR GAP208/10/2302 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100523 Keywords : infrared- laser spectroscopy * high-temperature pyrolysis * amorphous-carbon films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.771, year: 2012

  9. ARGON RECOIL ION ELECTRON CAPTURE FROM NEUTRAL ARGON AND HELIUM STUDIED BY TIME RESOLVED V.U.V. SPECTROSCOPY

    OpenAIRE

    Lesteven-Vaisse, I.; Chantepie, M.; Folkmann, F.; Lecler, D.; Ben Sitel, A.

    1989-01-01

    Electron capture phenomena in recoil ion V.U.V. spectroscopy are tested through the evolution of the observed argon spectrum by introduction of helium in addition to argon in the collision chamber. Taking into account these mixed gas data by the time-differential method and using decay time analysis, an improved analysis of argon recoil ion V.U.V. radiation is presented.

  10. Time-resolved characterization of a filamentary argon discharge at atmospheric pressure in a capillary using emission and absorption spectroscopy

    Science.gov (United States)

    Schröter, Sandra; Pothiraja, Ramasamy; Awakowicz, Peter; Bibinov, Nikita; Böke, Marc; Niermann, Benedikt; Winter, Jörg

    2013-11-01

    An argon/nitrogen (0.999/0.001) filamentary pulsed discharge operated at atmospheric pressure in a quartz tube is characterized using voltage-current measurements, microphotography, optical emission spectroscopy (OES) and absorption spectroscopy. Nitrogen is applied as a sensor gas for the purpose of OES diagnostic. The density of argon metastable atoms Ar(3P2) is determined using tunable diode laser absorption spectroscopy (TDLAS). Using a plasma chemical model the measured OES data are applied for the characterization of the plasma conditions. Between intense positive pulses the discharge current oscillates with a damped amplitude. It is established that an electric current flows in this discharge not only through a thin plasma filament that is observed in the discharge image but also through the whole cross section of the quartz tube. A diffuse plasma fills the quartz tube during a time between intense current pulses. Ionization waves are propagating in this plasma between the spike and the grounded area of the tube producing thin plasma channels. The diameter of these channels increases during the pause between the propagation of ionization waves probably because of thermal expansion and diffusion. Inside the channels electron densities of ˜2 × 1013 cm-3, argon metastable densities ˜1014 cm-3 and a reduced electric field about 10 Td are determined.

  11. Charge carrier mobility in poly[methyl(phenyl)silylene] studied by time-resolved terahertz spectroscopy and molecular modeling

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Kratochvílová, Irena; Kužel, Petr; Šebera, Jakub; Kochalska, Anna; Nožár, Juraj; Nešpůrek, Stanislav

    2011-01-01

    Roč. 13, č. 7 (2011), s. 2850-2856. ISSN 1463-9076 R&D Projects: GA ČR(CZ) GP202/09/P099; GA ČR GA203/08/1594; GA AV ČR KAN401770651; GA MŠk LC512; GA ČR(CZ) GAP304/10/1951 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40500505 Keywords : molecular electronics * THz spectroscopy * charge carrier mobility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.573, year: 2011

  12. Employing Time-Resolved Terahertz Spectroscopy to Analyze Carrier Dynamics in Cu2ZnSn(S,Se)4 Absorber Layers

    Science.gov (United States)

    Baxter, Jason; Guglietta, Glenn; Li, Siming; Roy Choudhury, Kaushik; Caspar, Jonathan; Bishop, Douglas; Lloyd, Michael; McCandless, Brian

    We report the application of time-resolved terahertz spectroscopy (TRTS) to measure photoexcited carrier lifetimes and mobility, and to determine recombination mechanisms in Cu2ZnSn(S,Se)4 (CZTSSe) thin films and single crystals. Ultrafast time resolution permits tracking the evolution of carrier density to determine recombination rates and mechanisms. The carrier generation profile was manipulated by varying the photoexcitation wavelength and fluence to distinguish between surface, Shockley-Read-Hall (SRH), radiative, and Auger recombination mechanisms and determine rate constants. Surface and SRH recombination are the dominant mechanisms for the air/CZTSSe/SiO2/Si film stack. Diffusion to, and then recombination at, the air-CZTSSe interface occurred on the order of 100 picoseconds, while SRH recombination lifetimes were 1 - 2 nanoseconds. Analogous measurements on single crystals reveal the effects of eliminating grain boundaries, reducing point defects and secondary phases, and applying surface treatments to reduce surface recombination velocity. TRTS measurements can provide information that is complementary to conventional time-resolved photoluminescence measurements and can direct the design of efficient thin film photovoltaics. Ref: Guglietta et al., APL, 2014. Nsf DMR-1507988.

  13. Mapping of calf muscle oxygenation and haemoglobin content during dynamic plantar flexion exercise by multi-channel time-resolved near-infrared spectroscopy

    International Nuclear Information System (INIS)

    A compact and fast multi-channel time-resolved near-infrared spectroscopy system for tissue oximetry was developed. It employs semiconductor laser and fibre optics for delivery of optical signals. Photons are collected by eight 1 mm fibres and detected by a multianode photomultiplier. A time-correlated single photon counting board is used for the parallel acquisition of time-resolved reflectance curves. Estimate of the reduced scattering coefficient is achieved by fitting with a standard model of diffusion theory, while the modified Lambert-Beer law is used to assess the absorption coefficient. In vivo measurements were performed on five healthy volunteers to monitor spatial changes in calf muscle (medial and lateral gastrocnemius; MG, LG) oxygen saturation (SmO2) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO2 was 73.0 ± 0.9 and 70.5 ± 1.7% in MG and LG, respectively (P = 0.045). At the end of the exercise, SmO2 decreased (69.1 ± 1.8 and 63.8 ± 2.1% in MG and LG, respectively; P 2 and tHb

  14. Mapping of calf muscle oxygenation and haemoglobin content during dynamic plantar flexion exercise by multi-channel time-resolved near-infrared spectroscopy

    Science.gov (United States)

    Torricelli, Alessandro; Quaresima, Valentina; Pifferi, Antonio; Biscotti, Giovanni; Spinelli, Lorenzo; Taroni, Paola; Ferrari, Marco; Cubeddu, Rinaldo

    2004-03-01

    A compact and fast multi-channel time-resolved near-infrared spectroscopy system for tissue oximetry was developed. It employs semiconductor laser and fibre optics for delivery of optical signals. Photons are collected by eight 1 mm fibres and detected by a multianode photomultiplier. A time-correlated single photon counting board is used for the parallel acquisition of time-resolved reflectance curves. Estimate of the reduced scattering coefficient is achieved by fitting with a standard model of diffusion theory, while the modified Lambert-Beer law is used to assess the absorption coefficient. In vivo measurements were performed on five healthy volunteers to monitor spatial changes in calf muscle (medial and lateral gastrocnemius; MG, LG) oxygen saturation (SmO2) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO2 was 73.0 ± 0.9 and 70.5 ± 1.7% in MG and LG, respectively (P = 0.045). At the end of the exercise, SmO2 decreased (69.1 ± 1.8 and 63.8 ± 2.1% in MG and LG, respectively; P muscle SmO2 and tHb.

  15. Time-Resolved Spectroscopy of the 3 Brightest and Hardest Short Gamma-Ray Bursts Observed with the FGST Gamma-Ray Burst Monitor

    CERN Document Server

    Guiriec, Sylvain; Connaugthon, Valerie; Kara, Erin; Daigne, Frederic; Kouveliotou, Chryssa; van der Horst, Alexander J; Paciesas, William; Meegan, Charles A; Bhat, P N; Foley, Suzanne; Bissaldi, Elisabetta; Burgess, Michael; Chaplin, Vandiver; Diehl, Roland; Fishman, Gerald; Gibby, Melissa; Giles, Misty; Goldstein, Adam; Greiner, Jochen; Gruber, David; von Kienlin, Andreas; Kippen, Marc; McBreen, Sheila; Preece, Robert; Rau, Arne; Tierney, Dave; Wilson-Hodge, Colleen

    2010-01-01

    From July 2008 to October 2009, the Gamma-ray Burst Monitor (GBM) on board the Fermi Gamma-ray Space Telescope (FGST) has detected 320 Gamma-Ray Bursts (GRBs). About 20% of these events are classified as short based on their T90 duration below 2 s. We present here for the first time time-resolved spectroscopy at timescales as short as 2 ms for the three brightest short GRBs observed with GBM. The time-integrated spectra of the events deviate from the Band function, indicating the existence of an additional spectral component, which can be fit by a power-law with index ~-1.5. The time-integrated Epeak values exceed 2 MeV for two of the bursts, and are well above the values observed in the brightest long GRBs. Their Epeak values and their low-energy power-law indices ({\\alpha}) confirm that short GRBs are harder than long ones. We find that short GRBs are very similar to long ones, but with light curves contracted in time and with harder spectra stretched towards higher energies. In our time-resolved spectrosco...

  16. On time resolved gas temperature measurements in a pulsed dc plasma using quantum cascade laser absorption spectroscopy

    International Nuclear Information System (INIS)

    With a time resolution of 33 µs, the gas temperature in a pulsed dc air plasma admixed with 0.8% NO has been measured by quantum cascade laser absorption spectroscopy (QCLAS). For this purpose, the temperature dependent intensity ratios of two absorption structures of NO at 1900 cm−1 (5.26 µm) have been used. The QCLAS system worked in the Intra Pulse Mode with a pulse repetition frequency of 30 kHz leading to a spectrum recorded each 33 µs. In a low pressure discharge, the influence of nonlinear absorption phenomena causing strong distorted absorption structures of NO has been taken into account by a calibration routine based on tabulated line strengths. Different mean plasma currents have been applied to the discharge leading to gas temperature values ranging from about 300 K up to about 500 K. (paper)

  17. In-situ analysis of fruit anthocyanins by means of total internal reflectance, continuous wave and time-resolved spectroscopy

    Science.gov (United States)

    Zude, Manuela; Spinelli, Lorenzo; Dosche, Carsten; Torricelli, Alessandro

    2009-08-01

    In sweet cherry (Prunus avium), the red pigmentation is correlated with the fruit maturity stage and can be measured by non-invasive spectroscopy. In the present study, the influence of varying fruit scattering coefficients on the fruit remittance spectrum (cw) were corrected with the effective pathlength and refractive index in the fruit tissue obtained with distribution of time-of-flight (DTOF) readings and total internal reflection fluorescence (TIRF) analysis, respectively. The approach was validated on fruits providing variation in the scattering coefficient outside the calibration sample set. In the validation, the measuring uncertainty when non-invasively analyzing fruits with cw method in comparison with combined application of cw, DTOF, and TIRF measurements showed an increase in r2 up to 22.7 % with, however, high errors in all approaches.

  18. Nonresonant ionization of oxygen molecules by femtosecond pulses: Plasma dynamics studied by time-resolved terahertz spectroscopy

    International Nuclear Information System (INIS)

    We show that optical pump-terahertz probe spectroscopy is a direct experimental tool for exploring laser-induced ionization and plasma formation in gases. Plasma was produced in gaseous oxygen by focused amplified femtosecond pulses. The ionization mechanisms at 400- and 800-nm excitation wavelengths differ significantly being primarily of a multiphoton character in the former case and a strong-field process in the latter case. The generation of the plasma in the focal volume of the laser and its expansion on subnanosecond time scale is directly monitored through its density-dependent susceptibility. A Drude model used to evaluate the plasma densities and electron-scattering rates successfully captures the observations for a wide range of pump intensities. In addition, rotational fingerprints of molecular and ionic species were also observed in the spectra

  19. Time-resolved study of a pulsed dc discharge using quantum cascade laser absorption spectroscopy: NO and gas temperature kinetics

    International Nuclear Information System (INIS)

    In a pulsed dc discharge of an Ar-N2 mixture containing 0.91% of NO the kinetics of the destruction of NO has been studied under static and flowing conditions, i.e. in a closed and open discharge tube (p = 266 Pa). For this purpose quantum cascade laser absorption spectroscopy (QCLAS) in the infrared spectral range has been applied as a new approach for fast in situ plasma diagnostics which is capable of achieving a time resolution below 100 ns. The time decay of the NO concentration was measured in single discharge pulses of 1 ms duration. Additionally, the temporal behaviour of the electric field and the applied power was followed during the pulse. The comparison of the time evolution of the NO concentration under static and flowing conditions and simplified model calculations enabled an analysis of the dynamics of the plasma heating to be made. The temperature increase during the pulse is below 40 K, but has a strong influence on the line strength of the NO absorption line. The apparent decrease in the NO concentration in a single pulse of about 20% is due to the heating of the gas which in turn makes the line strength vary while the concentration remains constant for several successive pulses. Therefore the QCLAS measurements combined with model calculations are a powerful non-invasive temperature probe with a remarkable time resolution approaching the sub-microsecond time scale

  20. Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(II) spin crossover complexes

    DEFF Research Database (Denmark)

    Døssing, Anders Rørbæk; Wolf, Matthias M. N.; Gross, Ruth;

    2008-01-01

      The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive...... infrared difference bands between 1000 and 1065 cm-1 that appear within the instrumental system response time of 350 fs after excitation at 387 nm display the formation of the vibrationally unrelaxed and hot high-spin 5T2 state. Vibrational relaxation is observed and characterized by the time constants 9.......4 ± 0.7 ps for [Fe(btpa)](PF6)2/acetone and 12.7 ± 0.7 ps for both [Fe(btpa)](PF6)2/acetonitrile and [Fe(b(bdpa)](PF6)2/acetonitrile. Vibrational analysis has been performed via DFT calculations of the low-spin and high-spin state normal modes of both compounds as well as their respective infrared...

  1. Effects of aging on working memory performance and prefrontal cortex activity:A time-resolved spectroscopy study

    Institute of Scientific and Technical Information of China (English)

    Jie Shi; Wenjing Zhou; Tongchao Geng; Huancong Zuo; Masahiro Tanida; Kaoru Sakatani

    2016-01-01

    Objective:This study aimed to employ time‐resolved spectroscopy (TRS) to explore age‐related differences in prefrontal cortex (PFC) activity while subjects performed a working memory task. Methods:We employed TRS to measure PFC activity in ten healthy younger and ten healthy older subjects while they performed a working memory (WM) task. All subjects performed the Sternberg test (ST) in which the memory‐set size varied between one and six digits. Using TRS, we recorded changes in cerebral blood oxygenation as a measure of changes in PFC activity during the task. In order to identify left/right asymmetry of PFC activity during the working memory task, we calculated the laterality score, i.e.,Δoxy‐Hb (rightΔoxy‐Hb—leftΔoxy‐Hb);positive values indicate greater activity in the right PFC, while negative values indicate greater activity in the left PFC. Results:During the ST, statistical analyses showed no significant differences between the younger and older groups in accuracy for low memory‐load and high memory‐load. In high memory‐load tasks, however, older subjects were slower than younger subjects (P Conclusions: The present results are consistent with the hemispheric asymmetry reduction in older adults (HAROLD) model;working memory tasks cause asymmetrical PFC activation in younger adults, while older adults tend to show reduced hemispheric lateralization.

  2. Toward Femtosecond Time-Resolved Inner-Shell Transient Absorption Spectroscopy of Ultrafast Dynamics in Sulfur-Containing Molecules

    Science.gov (United States)

    Lin, Ming-Fu; Neumark, Daniel; Leone, Stephen; Gessner, Oliver

    2013-05-01

    Sulfur-containing compounds play an important role in many applications such as polythiophene-based organic solar cells or the removal of sulfur compounds by hydrodesulfurization in the petroleum industry. Ultrafast relaxation dynamics (e.g. dissociation, internal conversion and intersystem crossing) of sulfur-containing molecules after photoexcitation have attracted considerable attention as a pathway to a better understanding of the fundamental chemistry of these systems. The novel technique of extreme ultraviolet (XUV) femtosecond transient absorption spectroscopy provides real-time access to the time-dependent structure and transient electronic states of molecules in the vicinity of a specific atom. The usable photon energy range of a high-order harmonic based XUV transient absorption setup has been extended up to 180 eV, enabling measurements in the vicinity of the sulfur 2p edge (165 eV). This new capability opens the route to monitor ultrafast intramolecular dynamics from the unique perspective of well-localized sulfur atoms. Preliminary results will be presented on the photoinduced ultrafast ring-opening, dissociation and vibrational relaxation dynamics in gaseous thiophene (C4H4S) and carbon disulfide (CS2) . Work supported by DOE DE-AC02-05CH11231.

  3. Time-resolved site-selection spectroscopy investigation of Y3(Al/sub 1-x/Ga/sub x/)5O12 : Nd3+ crystals

    International Nuclear Information System (INIS)

    We have used selective laser excitation techniques to investigate the spectroscopic properties of Nd3+ ions in Y3(Al/sub 1-x/Ga/sub x/)5O12 crystals and found the mixed crystal nature of the host produced both distinct structure and inhomogeneous broadening in the Nd3+ spectra. We employed time-resolved spectroscopy measurements to characterize energy transfer between Nd ions in nonequivalent crystal field sites and the results are consistent with the migration of energy among Nd ions in the dominant type of site with trapping occurring at Nd ions in defect sites. The migration and trapping processes require thermal activation and are consistent with a two-phonon assisted energy transfer mechanism. The efficiency of energy transfer is greater in mixed crystals than in unmixed garnet hosts, and it is shown that this is associated with the increase in the transition matrix elements in the mixed crystals

  4. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, Nils; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2010-05-02

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  5. Photodissociation of CH3CHO at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Verification of roaming and triple fragmentation

    Science.gov (United States)

    Hung, Kai-Chan; Tsai, Po-Yu; Li, Hou-Kuan; Lin, King-Chuen

    2014-02-01

    By using time-resolved Fourier-transform infrared emission spectroscopy, the HCO fragment dissociated from acetaldehyde (CH3CHO) at 248 nm is found to partially decompose to H and CO. The fragment yields are enhanced by the Ar addition that facilitates the collision-induced internal conversion. The channels to CH2CO + H2 and CH3CO + H are not detected significantly. The rotational population distribution of CO, after removing the Ar collision effect, shows a bimodal feature comprising both low- and high-rotational (J) components, sharing a fraction of 19% and 81%, respectively, for the vibrational state v = 1. The low-J component is ascribed to both roaming pathway and triple fragmentation. They are determined to have a branching ratio of 0.06, respectively, relative to the whole v = 1 population. The CO roaming is accompanied by a highly vibrational population of CH4 that yields a vibrational bimodality.

  6. Europium(III) complexed by HPSEC size-fractions of a vertisol humic acid: small differences evidenced by time-resolved luminescence spectroscopy.

    Science.gov (United States)

    Reiller, Pascal E; Brevet, Julien; Nebbioso, Antonio; Piccolo, Alessandro

    2011-03-01

    The size fractionation of a humic acid (HA) by high performance size exclusion chromatography (HPSEC) was used as a proxy for the filtration effect during HA transport through a porous medium with minimum specific chemical interactions. The modification of the Eu(III)-HA complexes' formation with the different size-fractions, as compared to the bulk HA, was studied in time-resolved luminescence spectroscopy (TRLS). Clear modifications in Eu(III)-HA complexes' structures were shown and related to the molecular characteristics of the separated size-fractions. The properties of most of size-fractions did not induce a major alteration of the affinity towards Eu(III). Only the most hydrophilic fractions eluted in the tail of the chromatographic peak, representing about 11% of total fractions-weight, gave some significantly different parameters. Using a simplistic complexation model, it was found that the available complexation sites decreased with the size reduction of humic fractions. PMID:21242102

  7. Time-resolved soft-x-ray spectroscopy of a magnetic octupole transition in nickel-like xenon, cesium, and barium ions

    Energy Technology Data Exchange (ETDEWEB)

    Trabert, E; Beiersdorfer, P; Brown, G V; Boyce, K; Kelley, R L; Kilbourne, C A; Porter, F S; Szymkowiak, A

    2005-11-11

    A microcalorimeter with event mode capability for time-resolved soft-x-ray spectroscopy, and a high-resolution flat-field EUV spectrometer have been employed at the Livermore EBIT-I electron beam ion trap for observations and wavelength measurements of M1, E2, and M3 decays of long-lived levels in the Ni-like ions Xe{sup 26+}, Cs{sup 27+}, and Ba{sup 28+}. Of particular interest is the lowest excited level, 3d{sup 9}4s {sup 3}D{sub 3}, which can only decay via a magnetic octupole (M3) transition. For this level in Xe an excitation energy of (590.40 {+-} 0.03eV) and a level lifetime of (11.5 {+-} 0.5 ms) have been determined.

  8. Surface vibrational relaxation of N2 studied by CO2 titration with time-resolved quantum cascade laser absorption spectroscopy

    International Nuclear Information System (INIS)

    A new method for determination of the wall de-excitation probability γN2 of vibrationally excited N2 on different surfaces exposed to low-pressure plasmas has been developed. A short dc discharge pulse of only a few milliseconds was applied to a mixture containing 0.05-1% of CO2 in N2 at a pressure of 133 Pa. Due to a nearly resonant fast vibrational transfer between N2(v) and the asymmetric ν3 mode of CO2 the vibrational excitation of these titrating molecules is an image of the degree of vibrational excitation of N2. In the afterglow, the vibrational relaxation of CO2 was monitored in situ using quantum cascade laser absorption spectroscopy. The experimental results were interpreted in terms of a numerical model of non-equilibrium vibrational kinetics in CO2-N2 mixtures. Heterogeneous relaxation was the main quenching process of N2(v) under the conditions of this study, which allowed determination of the value of γN2 from the best agreement between the experiment and the model. The new method is suitable for γN2 determination in a single plasma pulse with the discharge tube surface pretreated by a low-pressure plasma. The relaxation probability of the first vibrational level of nitrogen γ1 = (1.1 ± 0.15) × 10-3 found for Pyrex and silica is in reasonable agreement with the literature data. Using the new technique the N2(v = 1) quenching probability was measured on TiO2 surface, γ1 = (9 ± 1) × 10-3. A linear enhancement of the N2(v) wall deactivation probability with an increase in the admixture of CO2 was observed for all studied materials. In order to explain this effect, a vibrational energy transfer mechanism between N2(v) and adsorbed CO2 is proposed. (paper)

  9. Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples Following Pulse Radiolysis

    International Nuclear Information System (INIS)

    Pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is a powerful method for rapidly generating reduced or oxidized species and other free radicals in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. However, it is often difficult to identify the transient intermediates definitively due to a lack of structural information in the spectral bands. Time-resolved vibrational spectroscopy offers the structural specificity necessary for mechanistic investigations but has received only limited application in pulse radiolysis experiments. For example, time-resolved infrared (TRIR) spectroscopy has only been applied to a handful of gas-phase studies, limited mainly by several technical challenges. We have exploited recent developments in commercial external-cavity quantum cascade laser (EC-QCL) technology to construct a nanosecond TRIR apparatus that has allowed, for the first time, TRIR spectra to be recorded following pulse radiolysis of condensed-phase samples. Near single-shot sensitivity of DeltaOD <1 x 10(-3) has been achieved, with a response time of <20 ns. Using two continuous-wave EC-QCLs, the current apparatus covers a probe region from 1890-2084 cm(-1), and TRIR spectra are acquired on a point-by-point basis by recording transient absorption decay traces at specific IR wavelengths and combining these to generate spectral time slices. The utility of the apparatus has been demonstrated by monitoring the formation and decay of the one-electron reduced form of the CO(2) reduction catalyst, (Re(I)(bpy)(CO)(3)(CH(3)CN))(+), in acetonitrile with nanosecond time resolution following pulse radiolysis. Characteristic red-shifting of the nu(CO) IR bands confirmed that one-electron reduction of the complex took place. The availability of

  10. Hollow plasmonic antennas for broadband SERS spectroscopy

    Directory of Open Access Journals (Sweden)

    Gabriele C. Messina

    2015-02-01

    Full Text Available The chemical environment of cells is an extremely complex and multifaceted system that includes many types of proteins, lipids, nucleic acids and various other components. With the final aim of studying these components in detail, we have developed multiband plasmonic antennas, which are suitable for highly sensitive surface enhanced Raman spectroscopy (SERS and are activated by a wide range of excitation wavelengths. The three-dimensional hollow nanoantennas were produced on an optical resist by a secondary electron lithography approach, generated by fast ion-beam milling on the polymer and then covered with silver in order to obtain plasmonic functionalities. The optical properties of these structures have been studied through finite element analysis simulations that demonstrated the presence of broadband absorption and multiband enhancement due to the unusual geometry of the antennas. The enhancement was confirmed by SERS measurements, which showed a large enhancement of the vibrational features both in the case of resonant excitation and out-of-resonance excitation. Such characteristics indicate that these structures are potential candidates for plasmonic enhancers in multifunctional opto-electronic biosensors.

  11. Study on the interaction of phthalate esters to human serum albumin by steady-state and time-resolved fluorescence and circular dichroism spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaoyun [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Wang, Zhaowei [College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Zhou, Ximin; Wang, Xiaoru [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen, Xingguo, E-mail: chenxg@lzu.edu.cn [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-09-15

    Highlights: {center_dot} Molecular docking revealed PAEs to be located in the hydrophobic pocket of HSA. {center_dot} HSA-DMP had one class of binding sites while HSA-BBP and HSA-DEHP had two types. {center_dot} Hydrophobic and hydrogen interactions dominated in the association of HSA-PAEs. {center_dot} The lifetime of Trp residue of HSA decreased after the addition of PAEs. {center_dot} The presences of PAEs could alter the second structure of HSA. - Abstract: Phthalate esters (PAEs) are globally pervasive contaminants that are considered to be endocrine disruptor chemicals and toxic environmental priority pollutants. In this paper, the interactions between PAEs and human serum albumin (HSA) were examined by molecular modelling, steady state and time-resolved fluorescence, ultraviolet-visible spectroscopy (UV-vis) and circular dichroism spectroscopy (CD). The association constants between PAEs and HSA were determined using the Stern-Volmer and Scatchard equations. The binding of dimethyl phthalate (DMP) to HSA has a single class of binding site and its binding constants (K) are 4.08 x 10{sup 3}, 3.97 x 10{sup 3}, 3.45 x 10{sup 3}, and 3.20 x 10{sup 3} L mol{sup -1} at 289, 296, 303, and 310 K, respectively. The Stern-Volmer and Scatchard plots both had two regression curves for HSA-butylbenzyl phthalate (BBP) and HSA-di-2-ethylhexyl phthalate (DEHP), which indicated that these bindings were via two types of binding sites: the numbers of binding site for the first type were lower than for the second type. The binding constants of the first type binding site were higher than those of the second type binding site at corresponding temperatures, the results suggesting that the first type of binding site had high affinity and the second binding site involved other sites with lower binding affinity and selectivity. The thermodynamic parameters of the binding reactions ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) were measured, and they indicated the presences

  12. Study on the interaction of phthalate esters to human serum albumin by steady-state and time-resolved fluorescence and circular dichroism spectroscopy

    International Nuclear Information System (INIS)

    Highlights: · Molecular docking revealed PAEs to be located in the hydrophobic pocket of HSA. · HSA-DMP had one class of binding sites while HSA-BBP and HSA-DEHP had two types. · Hydrophobic and hydrogen interactions dominated in the association of HSA-PAEs. · The lifetime of Trp residue of HSA decreased after the addition of PAEs. · The presences of PAEs could alter the second structure of HSA. - Abstract: Phthalate esters (PAEs) are globally pervasive contaminants that are considered to be endocrine disruptor chemicals and toxic environmental priority pollutants. In this paper, the interactions between PAEs and human serum albumin (HSA) were examined by molecular modelling, steady state and time-resolved fluorescence, ultraviolet-visible spectroscopy (UV-vis) and circular dichroism spectroscopy (CD). The association constants between PAEs and HSA were determined using the Stern-Volmer and Scatchard equations. The binding of dimethyl phthalate (DMP) to HSA has a single class of binding site and its binding constants (K) are 4.08 x 103, 3.97 x 103, 3.45 x 103, and 3.20 x 103 L mol-1 at 289, 296, 303, and 310 K, respectively. The Stern-Volmer and Scatchard plots both had two regression curves for HSA-butylbenzyl phthalate (BBP) and HSA-di-2-ethylhexyl phthalate (DEHP), which indicated that these bindings were via two types of binding sites: the numbers of binding site for the first type were lower than for the second type. The binding constants of the first type binding site were higher than those of the second type binding site at corresponding temperatures, the results suggesting that the first type of binding site had high affinity and the second binding site involved other sites with lower binding affinity and selectivity. The thermodynamic parameters of the binding reactions (ΔGo, ΔHo and ΔSo) were measured, and they indicated the presences of hydrophobic forces and hydrogen interactions in the PAEs-HSA interactions, which agreed well with the results

  13. Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.;

    1996-01-01

    The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...... studies were carried out at pressures of 250-1000 mbar SF6 and temperatures of 298 and 341 K, where the formation of FNO was studied by monitoring the transient absorption of FNO at 310.5 nm. The observed pressure dependence is represented in terms of a fall-off curve with the following values of the...... limiting high- and low-pressure rate coefficients, k(rec,infinity) = (2.5 +/- 0.8) x 10(10) M(-1) s(-1) and k(rec,0)/[SF6] = (1.5 +/- 0.3) x 10(11) x (T/300)(-1.0) M(-2) s(-1) in the temperature range 200-400 K, and with the broadening factor, F-cent = 0.878 at 298 K....

  14. Measurements of plasma temperature and electron density in laser-induced copper plasma by time-resolved spectroscopy of neutral atom and ion emissions

    Indian Academy of Sciences (India)

    V K Unnikrishnan; Kamlesh Alti; V B Kartha; C Santhosh; G P Gupta; B M Suri

    2010-06-01

    Plasma produced by a 355 nm pulsed Nd:YAG laser with a pulse duration of 6 ns focussed onto a copper solid sample in air at atmospheric pressure is studied spectroscopically. The temperature and electron density characterizing the plasma are measured by time-resolved spectroscopy of neutral atom and ion line emissions in the time window of 300–2000 ns. An echelle spectrograph coupled with a gated intensified charge coupled detector is used to record the plasma emissions. The temperature is obtained using the Boltzmann plot method and the electron density is determined using the Saha– Boltzmann equation method. Both parameters are studied as a function of delay time with respect to the onset of the laser pulse. The results are discussed. The time window where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the laser-induced breakdown spectroscopy (LIBS) analysis of samples, is deduced from the temporal evolution of the intensity ratio of two Cu I lines. It is found to be 700–1000 ns.

  15. Development of a method for the in situ measurement of polycyclic aromatic hydrocarbons with time resolved laser fluorescence spectroscopy. Final report

    International Nuclear Information System (INIS)

    A method was developed for the detection of polycyclic aromatic hydrocarbons (PAH) in water on the basis of time resolved laser fluorescence spectroscopy. The detection of the sum of PAH in ground- and surfacewater is possible with high sensitivity and selectivity. The fluorescence of other substances like chlorophyll or dissolved organic matter is suppressed by a special choice of spectral and temporal windows. The method works without any sample preparation and gives the results in a very short time. On the basis of this method a first device was built with a sensitivity of 0,1 μg/1 PAH in water. The measuring time was less than one minute. The on site use of this prototype is possible because of the use of a battery driven nitrogen laser together with a notebook computer for system control The application of fiberoptic cables up to 30 meter length makes it possible to use the system for screening and monitoring of polluted areas both in existing wells and without any well by using geological probe techniques. (orig.)

  16. Local heterogeneity for a Eu3+-doped glass evidenced by time-resolved fluorescence spectroscopy coupled to scanning near-field optical microscopy

    International Nuclear Information System (INIS)

    Time-resolved fluorescence spectroscopy (TRFS) was applied to an aluminate glass sample doped with Eu3+ cation as a fluorescent probe of the chemical environment and local symmetry. Conventional far-field experiments revealed the presence of two different phases: an amorphous phase featured by a highly disordered environment surrounding the Eu3+ cation and a more ordered polycrystalline phase that exhibits a significant increase in the Eu3+ fluorescence decay time compared to that of the amorphous phase. Near-field fluorescence spectra and decay kinetics were recorded in the frontier region between the two phases using a home-built scanning near-field optical microscope. SNOM-TRFS experiments confirmed the presence of local heterogeneities in this part of the glass at a sub-micrometric spatial scale. Polycrystalline sites featured an important shear-force interaction with the probing fiber optic tip, a longer fluorescence decay time, and a higher Stark splitting of the 5D0 → 7FJ (J = 1-4) electronic transitions of the Eu3+ cations. (authors)

  17. Statistical Time-Resolved Spectroscopy: A higher fraction of short-period binaries for metal-rich F-type dwarfs in SDSS

    CERN Document Server

    Hettinger, T; Strader, J; Bickerton, S J; Beers, T C

    2015-01-01

    Stellar multiplicity lies at the heart of many problems in modern astrophysics, including the physics of star formation, the observational properties of unresolved stellar populations, and the rates of interacting binaries such as cataclysmic variables, X-ray binaries, and Type Ia supernovae. However, little is known about the stellar multiplicity of field stars in the Milky Way, in particular about the differences in the multiplicity characteristics between metal-rich disk stars and metal-poor halo stars. In this study we perform a statistical analysis of ~15,000 F-type dwarf stars in the Milky Way through time-resolved spectroscopy with the sub-exposures archived in the Sloan Digital Sky Survey. We obtain absolute radial velocity measurements through template cross-correlation of individual sub-exposures with temporal baselines varying from minutes to years. These sparsely sampled radial velocity curves are analyzed using Markov chain Monte Carlo techniques to constrain the very short-period binary fraction...

  18. In vivo validation of a bimodal technique combining time-resolved fluorescence spectroscopy and ultrasonic backscatter microscopy for diagnosis of oral carcinoma

    Science.gov (United States)

    Sun, Yang; Xie, Hongtao; Liu, Jing; Lam, Matthew; Chaudhari, Abhijit J.; Zhou, Feifei; Bec, Julien; Yankelevich, Diego R.; Dobbie, Allison; Tinling, Steven L.; Gandour-Edwards, Regina F.; Monsky, Wayne L.; Gregory Farwell, D.; Marcu, Laura

    2012-11-01

    Tissue diagnostic features generated by a bimodal technique integrating scanning time-resolved fluorescence spectroscopy (TRFS) and ultrasonic backscatter microscopy (UBM) are investigated in an in vivo hamster oral carcinoma model. Tissue fluorescence is excited by a pulsed nitrogen laser and spectrally and temporally resolved using a set of filters/dichroic mirrors and a fast digitizer, respectively. A 41-MHz focused transducer (37-μm axial, 65-μm lateral resolution) is used for UBM scanning. Representative lesions of the different stages of carcinogenesis show that fluorescence characteristics complement ultrasonic features, and both correlate with histological findings. These results demonstrate that TRFS-UBM provide a wealth of co-registered, complementary data concerning tissue composition and structure as it relates to disease status. The direct co-registration of the TRFS data (sensitive to surface molecular changes) with the UBM data (sensitive to cross-sectional structural changes and depth of tumor invasion) is expected to play an important role in pre-operative diagnosis and intra-operative determination of tumor margins.

  19. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    International Nuclear Information System (INIS)

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H]2− after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet 1A2u state and concomitant rise in population of the triplet 3A2u state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet 1A2u state takes only a few picoseconds, ESETD from the triplet 3A2u state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt2(μ-P2O5H2)4 + 2H]2− is the first example of a photoexcited multianion for which ESETD has been observed following ISC

  20. Time-resolved infrared diode laser spectroscopy of the ν1 (C O stretch) band of the CoCO radical

    Science.gov (United States)

    Ikeda, Seiki; Hikida, Toshihide; Tanaka, Takehiko; Tanaka, Keiichi

    2008-02-01

    Infrared spectrum of the cobalt carbonyl radical CoCO produced by the 193 nm excimer laser photolysis of cobalt tricarbonyl nitrosyl Co(CO) 3NO was observed by time-resolved diode laser spectroscopy. More than 600 lines were identified as belonging to the ν1 (C-O stretch) fundamental band, consisting of the Ω=5/2 and 3/2 subbands, and the associated hot bands 112, 101211, 101311, and 101222. The 2Δi electronic ground state of CoCO was experimentally confirmed. The ν1 band origins are 1974.172582(93) cm -1 and 1973.53178(14) cm -1 for the Ω=5/2 and 3/2 subbands, respectively. The rotational constant in the ground state was determined as B0=4427.146(50) MHz. The centrifugal distortion constant D0=1.1243(68) kHz was obtained for the Ω=5/2 substate of the ground state. The equilibrium rotational constant Be=4435.44(14) MHz was derived, together with the vibration-rotation interaction constants.

  1. Interaction of quinine sulfate with anionic micelles of sodium dodecylsulfate: A time-resolved fluorescence spectroscopy at different pH

    Science.gov (United States)

    Joshi, Sunita; Pant, Debi D.

    2015-09-01

    Photophysical behavior and rotational relaxation dynamics of quinine sulfate (QS) in anionic surfactant, sodium dodecylsulfate (SDS) at different pH have been studied using steady state and time resolved fluorescence spectroscopy. It has been observed that the cationic form of quinine sulfate (at pH 2) forms a fluorescent ion pair complex with the surfactant molecules at lower concentrations of surfactant. However, for higher concentrations of SDS, the probe molecules bind strongly with the micelles and reside at the water-micelle interface. At pH 7, QS is singly protonated in bulk aqueous solution. At lower concentrations of SDS aggregation between probe and surfactant molecules has been observed. However, for higher concentrations of SDS, an additional fluorescence peak corresponding to dicationic form of QS appears and this has been attributed to double protonation of the QS molecule in micellar solution. At pH 7, in the presence of SDS micelles, the photophysical properties of QS showed substantial changes compared to that in the bulk water solution. At pH 12, an increase in fluorescence intensity and lifetime has been observed and this has been attributed to the increase in radiative rate due to the incorporation of QS at the micelle-water interface. The local pH at micellar surface has been found different from the pH of bulk solution.

  2. ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

    Science.gov (United States)

    Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

    2013-11-01

    The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC. PMID:24083478

  3. Photolysis of n-butyl nitrite and isoamyl nitrite at 355 nm: A time-resolved Fourier transform infrared emission spectroscopy and ab initio study

    CERN Document Server

    Ji, Min; Zhang, Qun; Chen, Yang

    2009-01-01

    We report on the photodissociation dynamics study of n-butyl nitrite (n-C_4H_9ONO) and isoamyl nitrite ((CH_3)_2C_3H_5ONO) by means of time-resolved Fourier transform infrared (TR-FTIR) emission spectroscopy. The obtained TR-FTIR emission spectra of the nascent NO fragments produced in the 355-nm laser photolysis of the two alkyl nitrite species showed an almost identical rotational temperature and vibrational distributions of NO. In addition, a close resemblance between the two species was also found in the measured temporal profiles of the IR emission of NO and the recorded UV absorption spectra. The experimental results are consistent with our ab initio calculations using the time-dependent density functional theory at the B3LYP/6-311G(d,p) level, which indicate that the substitution of one of the two {gamma}-H atoms in n-C_4H_9ONO with a methyl group to form (CH_3)_2C_3H_5ONO has only a minor effect on the photodissociation dynamics of the two molecules.

  4. Study on vibrational relaxation dynamics of phenol–water complex by picosecond time-resolved IR-UV pump–probe spectroscopy in a supersonic molecular beam

    International Nuclear Information System (INIS)

    Graphical abstract: Picosecond IR-UV pump–probe study revealed a detailed energy dissipation route and its time scale from the energy put into the OH(OD) stretching vibration for the phenol–water hydrogen-bonded complex. - Abstract: A comparative study of vibrational energy relaxation (VER) between the monohydrated complexes of phenol-d0 and phenol-d1 is investigated in a supersonic molecular beam. The direct time-resolved measurement of energy redistribution from the phenolic OH/OD stretching mode of the phenol-d0-H2O/phenol-d1-D2O is performed by picosecond IR-UV pump–probe spectroscopy. Two complexes follow the same relaxation process that begins with the intramolecular vibrational energy redistribution (IVR) and the intermolecular vibrational energy redistribution (IVR), which is followed by the vibrational predissociation (VP). The difference in the relaxation lifetimes between them is discussed by anharmonic force field and RRKM calculations. Anharmonic analysis implies that intra- (IVR) and intermolecular (IVR) relaxations occur in parallel in the complexes. The RRKM-predicted dissociation (VP) lifetimes show qualitative agreement with the observed results, suggesting that VP takes place after the statistical energy distribution in the complexes

  5. Charge dynamics at heterojunctions for PbS/ZnO colloidal quantum dot solar cells probed with time-resolved surface photovoltage spectroscopy

    Science.gov (United States)

    Spencer, B. F.; Leontiadou, M. A.; Clark, P. C. J.; Williamson, A. I.; Silly, M. G.; Sirotti, F.; Fairclough, S. M.; Tsang, S. C. E.; Neo, D. C. J.; Assender, H. E.; Watt, A. A. R.; Flavell, W. R.

    2016-02-01

    Time-resolved laser-pump X-ray-photoemission-probe spectroscopy of a ZnO ( 10 1 ¯ 0 ) substrate with and without PbS quantum dots (QDs) chemically linked to the surface is performed, using laser photon energies resonant with and below the band gap energy of the substrate (λ = 372 and 640 nm, hν = 3.33 and 1.94 eV). Charge injection from the photoexcited QDs to ZnO is demonstrated through the change in the surface photovoltage of the ZnO substrate observed when the heterojunction is illuminated with 1.94 eV radiation. The measured carrier dynamics are limited by the persistent photoconductivity of ZnO, giving dark carrier lifetimes of the order of 200 μs in a depletion layer at the interface. The chemical specificity of soft X-rays is used to separately measure the charge dynamics in the quantum dots and the substrate, yielding evidence that the depletion region at the interface extends into the PbS QD layer.

  6. Spectral characterization of crude oil using fluorescence (synchronous and time-resolved) and NIR (Near Infrared Spectroscopy); Caracterizacao espectral do petroleo utilizando fluorescencia (sincronizada e resolvida no tempo) e NIR (Near Infrared Spectroscopy)

    Energy Technology Data Exchange (ETDEWEB)

    Falla Sotelo, F.; Araujo Pantoja, P.; Lopez-Gejo, J.; Le Roux, G.A.C.; Nascimento, C.A.O. [Universidade de Sao Paulo (USP), SP (Brazil). Dept. de Engenharia Quimica. Lab. de Simulacao e Controle de Processos; Quina, F.H. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Centro de Capacitacao e Pesquisa em Meio Ambiente (CEPEMA)

    2008-07-01

    The objective of the present work is to evaluate the performance of two spectroscopic techniques employed in the crude oil characterization: NIR spectroscopy and fluorescence spectroscopy (Synchronous fluorescence - SF and Time Resolved Fluorescence - TRF) for the development of correlation models between spectral profiles of crude oil samples and both physical properties (viscosity and API density) and physico-chemical properties (SARA analysis: Saturated, Aromatic, Resins and Asphaltenes). The better results for viscosity and density were obtained using NIR whose prediction capacity was good (1.5 cP and 0.5 deg API, respectively). For SARA analysis, fluorescence spectroscopy revealed its potential in the model calibration showing good results (R2 coefficients greater than 0.85). TRF spectroscopy had better performance than SF spectroscopy. (author)

  7. NI-49SMART SUCKER: NEXT GENERATION SMART SURGICAL TOOL FOR INTRAOPERATIVE BRAIN TUMOR RESECTION USING TIME RESOLVED LASER INDUCED FLUORESCENCE SPECTROSCOPY

    Science.gov (United States)

    Kittle, David S.; Butte, Pramod V.; Vasefi, Fartash; Patil, Chirag G.; Black, Keith

    2014-01-01

    Primary brain tumors are highly lethal tumors where surgical resection is the primary treatment of choice. It has been shown that survival rate is directly related to the extent of tumor resection. In order to aid the surgeon in achieving near-complete resection, novel technologies are required. Time-resolved laser induced fluorescence spectroscopy (TRLIFS) promises to be one such technology, where the tissue is excited using an ultra-short laser and the corresponding fluorescence intensity decay is captured. Based on the fluorescence spectrum and the decay characteristics at various color bands from TRLIFS, differentiation of tumor from the normal brain tissue is possible in real-time. We built a portable TRLIFS system using custom optics and hardware (laser excitation: 355nm, 400ps pulse width, 5 uJ/pulse; PMT detector: Photek, rise time 80 picoseconds; digitizer: 7 Giga-samples per second) which is capable of providing the results in real time (every 50 milliseconds). We have designed a custom probe which is attached to a Roton sucker "Smart sucker" to collect the data during surgical resection from patients at Cedars-Sinai Medical Center. The histopathological diagnosis of the site under study with TRLIFS is confirmed with a biopsy and H-E staining. We will present our preliminary data from human brain tumor samples collected in-vivo. Our preliminary study shows that TRLIFS is capable of classifying low grade tumors with high sensitivity and specificity. This study will also demonstrate the potential of using the TRLIFS system to enhance the surgical instrumentation, aiding surgeons in near-complete excision of tumors and bringing these instruments into the next generation of smart tools.

  8. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Energy Technology Data Exchange (ETDEWEB)

    Winghart, Marc-Oliver, E-mail: marc-oliver.winghart@kit.edu; Unterreiner, Andreas-Neil [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Yang, Ji-Ping [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); School of Sciences, Hefei University of Technology, Hefei 230009 (China); Vonderach, Matthias [Centre for Proteome Research, Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Huang, Dao-Ling; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Kruppa, Sebastian; Riehn, Christoph [Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Kappes, Manfred M., E-mail: manfred.kappes@kit.edu [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)

    2016-02-07

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  9. Stark-assisted population control of coherent CS(2) 4f and 5p Rydberg wave packets studied by femtosecond time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Knappenberger, Kenneth L; Lerch, Eliza-Beth W; Wen, Patrick; Leone, Stephen R

    2007-09-28

    A two-color (3+1(')) pump-probe scheme is employed to investigate Rydberg wave packet dynamics in carbon disulfide (CS(2) (*)). The state superpositions are created within the 4f and 5p Rydberg manifolds by three photons of the 400 nm pump pulse, and their temporal evolution is monitored with femtosecond time-resolved photoelectron spectroscopy using an 800 nm ionizing probe pulse. The coherent behavior of the non-stationary superpositions are observed through wavepacket revivals upon ionization to either the upper (12) or lower (32) spin-orbit components of CS(2) (+). The results show clearly that the composition of the wavepacket can be efficiently controlled by the power density of the excitation pulse over a range from 500 GWcm(2) to 10 TWcm(2). The results are consistent with the anticipated ac-Stark shift for 400 nm light and demonstrate an effective method for population control in molecular systems. Moreover, it is shown that Rydberg wavepackets can be formed in CS(2) with excitation power densities up to 10 TWcm(2) without significant fragmentation. The exponential 1e population decay (T(1)) of specific excited Rydberg states are recovered by analysis of the coherent part of the signal. The dissociation lifetimes of these states are typically 1.5 ps. However, a region exhibiting a more rapid decay ( approximately 800 fs) is observed for states residing in the energy range of 74 450-74 550 cm(-1), suggestive of an enhanced surface crossing in this region. PMID:17902914

  10. A comparative batch sorption and time-resolved laser fluorescence spectroscopy study on the sorption of Eu(III) and Cm(III) on synthetic and natural kaolinite

    International Nuclear Information System (INIS)

    Eu(III) and Cm(III) sorption onto synthetic and natural kaolinite (St. Austell, UK) were studied by batch sorption experiments and time-resolved laser fluorescence spectroscopy (TRLFS). All investigations were performed under argon atmosphere (O2 4 and 0.25 g/l. kaolinite were used as electrolyte and solid concentrations, respectively, throughout the study. Batch sorption experiments were performed with Eu(III), a homologue to trivalent actinides at three different metal ion concentrations between 6.6 x 10-8 and 6.6 x 10-6 M. pH-dependent sorption was found to be congruent for the two lowest Eu(III) concentrations (6.6 x 10-8 and 6.6 x 10-7 M) while a shift of the sorption distribution coefficient, Kd, to higher pH values was observed for the highest metal ion concentration (6.6 x 10-6 M). Furthermore, the natural kaolinite showed higher uptake of Eu(III) for the lowest metal ion concentration at pH -7 M Cm(III) as a luminescent probe. Four single component spectra could be extracted from the recorded emission spectra for both the synthetic and the natural kaolinite, with peak positions in average at 598.8, 602.7, 607.4 and 611.0 nm. The three first emission peaks appearing between pH 5 and 13 were assigned to three inner-sphere Cm-complexes. The fourth emission peak appearing in the alkaline pH range (> 9) is assumed to be a result of Cm(III) incorporation by a surface precipitate of hitherto unknown composition. (orig.)

  11. Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

    Science.gov (United States)

    Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

    2007-05-01

    Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein. PMID:17446273

  12. Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.; Ratajczak, E.

    The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics was...

  13. Time-resolved studies

    International Nuclear Information System (INIS)

    When new or more powerful probes become available that offer both shorter data-collection times and the opportunity to apply innovative approaches to established techniques, it is natural that investigators consider the feasibility of exploring the kinetics of time-evolving systems. This stimulating area of research not only can lead to insights into the metastable or excited states that a system may populate on its way to a ground state, but can also lead to a better understanding of that final state. Synchrotron radiation, with its unique properties, offers just such a tool to extend X-ray measurements from the static to the time-resolved regime. The most straight-forward application of synchrotron radiation to the study of transient phenomena is directly through the possibility of decreased data-collection times via the enormous increase in flux over that of a laboratory X-ray system. Even further increases in intensity can be obtained through the use of novel X-ray optical devices. Widebandpass monochromators, e.g., that utilize the continuous spectral distribution of synchrotron radiation, can increase flux on the sample several orders of magnitude over conventional X-ray optical systems thereby allowing a further shortening of the data-collection time. Another approach that uses the continuous spectral nature of synchrotron radiation to decrease data-collection times is the open-quote parallel data collectionclose quotes method. Using this technique, intensities as a function of X-ray energy are recorded simultaneously for all energies rather than sequentially recording data at each energy, allowing for a dramatic decrease in the data-collection time

  14. Sulfate complexation of trivalent lanthanides probed by nano-electro-spray mass spectrometry and time-resolved laser-induced fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Full text of publication follows: Sulfate complexation of lanthanides is of great interest to predict the speciation of radionuclides in natural environments. In the present work, the stability constants of sulfate complexes of trivalent lanthanide ions were investigated by two speciation techniques: nano-Electro-Spray Ionisation Mass Spectrometry (nano-ESI-MS) and Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS). TRLFS was used to study the Eu(III) speciation in the ionic conditions 0.02-0.05 mol/l H+ (H2SO4 / HClO4) and 0.4-2.0 mol/l Na+ (Na2SO4 / NaClO4). The data were interpreted with the EuSO4+ and Eu(SO4)2- species. To calculate the effect of the ionic medium on the complexation constants, all the major ions were taken into account through several ion-pair parameters, ε, of the Specific ion Interaction Theory (SIT). Several ε values were estimated by analogy using linear correlations, while ε(Eu3+, SO42-) was fitted to experimental data, since, to date, SIT coefficients between multicharged species are not reported. The formation constants proposed here confirm some of those previously measured for Ln(III) and An(III) by various experimental techniques. The TRLFS lifetimes measured for EuSO4+ and Eu(SO4)2- were found consistent with the replacement of one H2O molecule in the first coordination sphere of Eu3+ for each added SO42- ligand, suggesting monodentate SO42- coordination. Moreover, these results and equilibrium thermodynamics do not give credit that TRLFS and other spectroscopic techniques would provide stability constants of only inner sphere complexes while they are in equilibrium with possible outer sphere complexes. Besides, numerous La(III) species were observed in a gaseous phase by nano-ESI-MS from the analysis of HNO3 / H2SO4 aqueous solutions with low ionic strength. The mass spectra were interpreted according to the expected formation of LaSO4+(aq). Its formation constant was measured and compared well with the TRLFS results

  15. [Time resolved plasma spectroscopy of imploded gas-filled microballoons: The next generation]. Final technical report, 17 April 1995--30 September 1997

    Energy Technology Data Exchange (ETDEWEB)

    Hooper, C.F. Jr.

    1998-03-01

    use time-resolved K-shell Ar spectra from the implosions. Varying the relative concentration of Ar in DD provides an opportunity to study the combined and individual effects of ion motion and opacity on the Stark broadened line profiles. Appendix C addresses the use of high opacity Krypton lines to diagnose high temperature implosions, and provides additional detail about the effects of ion dynamics.

  16. Influence of pH and metal ion loading on the Cm(III) humate complexation. A time resolved laser fluorescence spectroscopy study

    International Nuclear Information System (INIS)

    Interaction of trivalent lanthanides and Cm(III) with humic acid (HA) (l0mg/L) is studied as a function of metal ion concentration (1 x 108 to 5 x 10-5 mol/L) and pH (2.5 to 7.0) in 0.01 mol/L NaClO4. Time resolved laser fluorescence spectroscopy (TRLFS) reveals a slight blue-shift/broadening of the fluorescence peak position for the Cm(III)-HA complex combined with an enhanced contribution of a short-lived fluorescence component with increasing metal ion loading and decreasing pH. Fluorescence decay for Cm(III)-HA is non-monoexponential under all investigated conditions and lifetimes can be described by assuming a short lived (τ = 61 μs) and a longer lived contribution (τ = 142 μs). These findings are explained by the existence of a certain heterogeneity in binding sites inducing slightly variable ligand-field splitting in the Cm(III)-HA complex. Batch experiments with a Eu(III)-HA solution contacted with a chelating resin reveal a decrease of the solid/liquid distribution coefficient by decreasing the occupancy of HA ligand sites from 4% to 0.2%. This observation indicates that complexation constants for the Eu(III)-HA complex vary with metal loading. Differences in related constants are, however, smaller than one order of magnitude. Variations in fluorescence lifetimes are interpreted as a consequence of increasing HA agglomeration at increasing metal loading and decreasing pH, thus leading to an enhanced local density of chromophoric groups close to the Cm(III) ion favouring non-radiative energy transition. HA agglomeration at low pH and increasing metal ion loading is well known from previous studies using flow-field flow fractionation (FFF) coupled to ICP-mass spectrometry and UV-Vis spectrophotometry. Our experimental results demonstrate the dynamic properties of metal-HA complexes depending on chemical conditions. (orig.)

  17. Folding dynamics of the Trp-cage miniprotein: evidence for a native-like intermediate from combined time-resolved vibrational spectroscopy and molecular dynamics simulations.

    Science.gov (United States)

    Meuzelaar, Heleen; Marino, Kristen A; Huerta-Viga, Adriana; Panman, Matthijs R; Smeenk, Linde E J; Kettelarij, Albert J; van Maarseveen, Jan H; Timmerman, Peter; Bolhuis, Peter G; Woutersen, Sander

    2013-10-01

    Trp-cage is a synthetic 20-residue miniprotein which folds rapidly and spontaneously to a well-defined globular structure more typical of larger proteins. Due to its small size and fast folding, it is an ideal model system for experimental and theoretical investigations of protein folding mechanisms. However, Trp-cage's exact folding mechanism is still a matter of debate. Here we investigate Trp-cage's relaxation dynamics in the amide I' spectral region (1530-1700 cm(-1)) using time-resolved infrared spectroscopy. Residue-specific information was obtained by incorporating an isotopic label ((13)C═(18)O) into the amide carbonyl group of residue Gly11, thereby spectrally isolating an individual 310-helical residue. The folding-unfolding equilibrium is perturbed using a nanosecond temperature-jump (T-jump), and the subsequent re-equilibration is probed by observing the time-dependent vibrational response in the amide I' region. We observe bimodal relaxation kinetics with time constants of 100 ± 10 and 770 ± 40 ns at 322 K, suggesting that the folding involves an intermediate state, the character of which can be determined from the time- and frequency-resolved data. We find that the relaxation dynamics close to the melting temperature involve fast fluctuations in the polyproline II region, whereas the slower process can be attributed to conformational rearrangements due to the global (un)folding transition of the protein. Combined analysis of our T-jump data and molecular dynamics simulations indicates that the formation of a well-defined α-helix precedes the rapid formation of the hydrophobic cage structure, implying a native-like folding intermediate, that mainly differs from the folded conformation in the orientation of the C-terminal polyproline II helix relative to the N-terminal part of the backbone. We find that the main free-energy barrier is positioned between the folding intermediate and the unfolded state ensemble, and that it involves the formation of

  18. Time-resolved spectroscopy of Bi.sup.3+./sup. centers in Y.sub.4./sub.Al.sub.2./sub.O.sub.9./sub..

    Czech Academy of Sciences Publication Activity Database

    Babin, Vladimir; Lipinska, L.; Mihóková, Eva; Nikl, Martin; Shalapska, T.; Suchocki, A.; Zazubovich, S.; Zhydachevskii, Ya.

    2015-01-01

    Roč. 46, Aug (2015), s. 104-108. ISSN 0925-3467 R&D Projects: GA ČR GAP204/12/0805 Institutional support: RVO:68378271 Keywords : time-resolved luminescence * excited state dynamics * Bi 3+ -doped Y 4 Al 2 O 9 Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.981, year: 2014

  19. Theory of sum-frequency generation spectroscopy of adsorbed molecules using the density matrix method-broadband vibrational sum-frequency generation and applications

    International Nuclear Information System (INIS)

    A generalized theory of frequency- and time-resolved vibrational sum-frequency generation (SFG) spectroscopy of adsorbates at surfaces is presented using the density matrix formalism. Our theoretical treatment is specifically aimed at addressing issues that accompany the relatively novel SFG approach using broadband infrared pulses. The ultrashort duration of these pulses makes them ideally suited for time-resolved investigations, for which we present a complete theoretical treatment. A second key characteristic of these pulses is their large bandwidth and high intensity, which allow for highly non-linear effects, including vibrational ladder climbing of surface vibrations. We derive general expressions relating the density matrix to SFG spectra, and apply these expressions to specific experimental results by solving the coupled optical Bloch equations of the density matrix elements. Thus, we can theoretically reproduce recent experimentally demonstrated hot band SFG spectra using femtosecond broadband infrared excitation of carbon monoxide (CO) on a Ru(001) surface

  20. Measurement of the rate of bimolecular electron spin relaxation between pairs of reactive radicals using time-resolved electron spin-echo spectroscopy

    International Nuclear Information System (INIS)

    The time-resolved electron spin echo (ESE) method has been employed to measure the bimolecular contribution to electron spin relaxation in the acetate radical xCH2CO-2, formed by pulse radiolysis. Time-resolved ESE signals from solutions containing up to 4 x 10-4 M initial radical concentrations were analyzed using Bloch equations modified to include the effects of strong Heisenberg exchange, chemical reaction, and CIDEP. It is found that the electron exchange rate is approx.3 times faster than the chemical reaction rate, contrary to a simple model involving only statistical factors which predicts equal rates for the two processes. It is also found that the CIDEP enhancement factor is independent of initial radical concentration over the ten fold range of concentrations studied

  1. Fluorescence-suppressed time-resolved Raman spectroscopy of pharmaceuticals using complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector

    OpenAIRE

    Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C.; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J.; Yliperttula, Marjo

    2015-01-01

    In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is ...

  2. Strategies for Complex Mixture Analysis in Broadband Microwave Spectroscopy.

    Science.gov (United States)

    Steber, Amanda L.; Neill, Justin L.; Muckle, Matthew T.; Pate, Brooks H.; Plusquellic, D. F.; Lattanzi, V.; Spezzano, S.; McCarthy, M. C.

    2010-06-01

    Broadband microwave spectra often contain overlapping spectra from a large number of species in the sample mixture, whether in the study of conformational isomers, molecular complexes, reaction products from reactive molecular sources (e.g., electrical discharge), or analysis of chemical mixtures. In these experiments, the identification of individual spectra in the full spectrum through pattern recognition becomes difficult when there is a high density of transitions. Strategies for extracting individual spectra from broadband measurements are discussed. Two approaches for microwave-microwave double resonance spectroscopy have been evaluated. One uses a transition-by-transition screening in a narrowband cavity spectrometer to identify an unknown spectrum and has a time advantage from the increased sensitivity of cavity spectroscopy. The second double-resonance approach uses a broadband spectral editing approach that gives a multiplex advantage in the detection. Both of these experimental techniques are combined with computer-aided assignment algorithms to make the spectral assignment in a minimum of double-resonance observations. The performance of spectral analysis solely using computer-aided assignment is also evaluated. The potential for fully automated spectral decomposition of the broadband spectrum of a complex mixture will be described.

  3. Broadband infrared vibrational nano-spectroscopy using thermal blackbody radiation.

    Science.gov (United States)

    O'Callahan, Brian T; Lewis, William E; Möbius, Silke; Stanley, Jared C; Muller, Eric A; Raschke, Markus B

    2015-12-14

    Infrared vibrational nano-spectroscopy based on scattering scanning near-field optical microscopy (s-SNOM) provides intrinsic chemical specificity with nanometer spatial resolution. Here we use incoherent infrared radiation from a 1400 K thermal blackbody emitter for broadband infrared (IR) nano-spectroscopy. With optimized interferometric heterodyne signal amplification we achieve few-monolayer sensitivity in phonon polariton spectroscopy and attomolar molecular vibrational spectroscopy. Near-field localization and nanoscale spatial resolution is demonstrated in imaging flakes of hexagonal boron nitride (hBN) and determination of its phonon polariton dispersion relation. The signal-to-noise ratio calculations and analysis for different samples and illumination sources provide a reference for irradiance requirements and the attainable near-field signal levels in s-SNOM in general. The use of a thermal emitter as an IR source thus opens s-SNOM for routine chemical FTIR nano-spectroscopy. PMID:26698997

  4. Frequency Comb Assisted Broadband Precision Spectroscopy with Cascaded Diode Lasers

    CERN Document Server

    Liu, Junqiu; Pfeiffer, Martin H P; Kordts, Arne; Kamel, Ayman N; Guo, Hairun; Geiselmann, Michael; Kippenberg, Tobias J

    2016-01-01

    Frequency comb assisted diode laser spectroscopy, employing both the accuracy of an optical frequency comb and the broad wavelength tuning range of a tunable diode laser, has been widely used in many applications. In this letter we present a novel method using cascaded frequency agile diode lasers, which allows extending the measurement bandwidth to 37.4 THz (1355 to 1630 nm) at MHz resolution with scanning speeds above 1 THz/s. It is demonstrated as a useful tool to characterize a broadband spectrum for molecular spectroscopy and in particular it enables to characterize the dispersion of integrated microresonators up to the fourth order.

  5. Structure of fenchone by broadband rotational spectroscopy.

    Science.gov (United States)

    Loru, Donatella; Bermúdez, Miguel A; Sanz, M Eugenia

    2016-08-21

    The bicyclic terpenoid fenchone (C10H16O, 1,3,3-trimethylbicyclo[2.2.1]heptan-2-one) has been investigated by chirped pulse Fourier transform microwave spectroscopy in the 2-8 GHz frequency region. The parent species and all heavy atom isotopologues have been observed in their natural abundance. The experimental rotational constants of all isotopic species observed have been determined and used to obtain the substitution (rs) and effective (r0) structures of fenchone. Calculations at the B3LYP, M06-2X, and MP2 levels of theory with different basis sets were carried out to check their performance against experimental results. The structure of fenchone has been compared with those of norbornane (bicyclo[2.2.1]heptane) and the norbornane derivatives camphor (1,7,7-trimethylbicyclo[2.2.1]heptan-2-one) and camphene (3,3-dimethyl-2-methylenebicyclo[2.2.1]heptane), both with substituents at C2. The structure of fenchone is remarkably similar to those of camphor and camphene. Comparison with camphor allows identification of changes in ∠CCC angles due to the different position of the methyl groups. All norbornane derivatives display similar structural changes with respect to norbornane. These changes mainly affect the bond lengths and angles of the six-membered rings, indicating that the substituent at C2 drives structural adjustments to minimise ring strain after its introduction. PMID:27544109

  6. X-ray Absorption Spectroscopy and Coherent X-ray Diffraction Imaging for Time-Resolved Investigation of the Biological Complexes: Computer Modelling towards the XFEL Experiment

    Science.gov (United States)

    Bugaev, A. L.; Guda, A. A.; Yefanov, O. M.; Lorenz, U.; Soldatov, A. V.; Vartanyants, I. A.

    2016-05-01

    The development of the next generation synchrotron radiation sources - free electron lasers - is approaching to become an effective tool for the time-resolved experiments aimed to solve actual problems in various fields such as chemistry’ biology’ medicine’ etc. In order to demonstrate’ how these experiments may be performed for the real systems to obtain information at the atomic and macromolecular levels’ we have performed a molecular dynamics computer simulation combined with quantum chemistry calculations for the human phosphoglycerate kinase enzyme with Mg containing substrate. The simulated structures were used to calculate coherent X-ray diffraction patterns’ reflecting the conformational state of the enzyme, and Mg K-edge X-ray absorption spectra, which depend on the local structure of the substrate. These two techniques give complementary information making such an approach highly effective for time-resolved investigation of various biological complexes, such as metalloproteins or enzymes with metal-containing substrate, to obtain information about both metal-containing active site or substrate and the atomic structure of each conformation.

  7. Photoelectron spectroscopy at a free-electron laser. Investigation of space-charge effects in angle-resolved and core-level spectroscopy and realizaton of a time-resolved core-level photoemission experiment

    Energy Technology Data Exchange (ETDEWEB)

    Marczynski-Buehlow, Martin

    2012-01-30

    The free-electron laser (FEL) in Hamburg (FLASH) is a very interesting light source with which to perform photoelectron spectroscopy (PES) experiments. Its special characteristics include highly intense photon pulses (up to 100 J/pulse), a photon energy range of 30 eV to 1500 eV, transverse coherence as well as pulse durations of some ten femtoseconds. Especially in terms of time-resolved PES (TRPES), the deeper lying core levels can be reached with photon energies up to 1500 eV with acceptable intensity now and, therefore, element-specific, time-resolved core-level PES (XPS) is feasible at FLASH. During the work of this thesis various experimental setups were constructed in order to realize angle-resolved (ARPES), core-level (XPS) as well as time-resolved PES experiments at the plane grating monochromator beamline PG2 at FLASH. Existing as well as newly developed systems for online monitoring of FEL pulse intensities and generating spatial and temporal overlap of FEL and optical laser pulses for time-resolved experiments are successfully integrated into the experimental setup for PES. In order to understand space-charge effects (SCEs) in PES and, therefore, being able to handle those effects in future experiments using highly intense and pulsed photon sources, the origin of energetic broadenings and shifts in photoelectron spectra are studied by means of a molecular dynamic N-body simulation using a modified Treecode Algorithm for sufficiently fast and accurate calculations. It turned out that the most influencing parameter is the ''linear electron density'' - the ratio of the number of photoelectrons to the diameter of the illuminated spot on the sample. Furthermore, the simulations could reproduce the observations described in the literature fairly well. Some rules of thumb for XPS and ARPES measurements could be deduced from the simulations. Experimentally, SCEs are investigated by means of ARPES as well as XPS measurements as a function of

  8. Photoelectron spectroscopy at a free-electron laser. Investigation of space-charge effects in angle-resolved and core-level spectroscopy and realizaton of a time-resolved core-level photoemission experiment

    International Nuclear Information System (INIS)

    The free-electron laser (FEL) in Hamburg (FLASH) is a very interesting light source with which to perform photoelectron spectroscopy (PES) experiments. Its special characteristics include highly intense photon pulses (up to 100 J/pulse), a photon energy range of 30 eV to 1500 eV, transverse coherence as well as pulse durations of some ten femtoseconds. Especially in terms of time-resolved PES (TRPES), the deeper lying core levels can be reached with photon energies up to 1500 eV with acceptable intensity now and, therefore, element-specific, time-resolved core-level PES (XPS) is feasible at FLASH. During the work of this thesis various experimental setups were constructed in order to realize angle-resolved (ARPES), core-level (XPS) as well as time-resolved PES experiments at the plane grating monochromator beamline PG2 at FLASH. Existing as well as newly developed systems for online monitoring of FEL pulse intensities and generating spatial and temporal overlap of FEL and optical laser pulses for time-resolved experiments are successfully integrated into the experimental setup for PES. In order to understand space-charge effects (SCEs) in PES and, therefore, being able to handle those effects in future experiments using highly intense and pulsed photon sources, the origin of energetic broadenings and shifts in photoelectron spectra are studied by means of a molecular dynamic N-body simulation using a modified Treecode Algorithm for sufficiently fast and accurate calculations. It turned out that the most influencing parameter is the ''linear electron density'' - the ratio of the number of photoelectrons to the diameter of the illuminated spot on the sample. Furthermore, the simulations could reproduce the observations described in the literature fairly well. Some rules of thumb for XPS and ARPES measurements could be deduced from the simulations. Experimentally, SCEs are investigated by means of ARPES as well as XPS measurements as a function of FEL pulse

  9. Broadband fitting approach for the application of supercontinuum broadband laser absorption spectroscopy to combustion environments

    Science.gov (United States)

    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. Time resolved techniques: An overview

    International Nuclear Information System (INIS)

    Synchrotron sources provide exceptional opportunities for carrying out time-resolved x-ray diffraction investigations. The high intensity, high angular resolution, and continuously tunable energy spectrum of synchrotron x-ray beams lend themselves directly to carrying out sophisticated time-resolved x-ray scattering measurements on a wide range of materials and phenomena. When these attributes are coupled with the pulsed time-structure of synchrotron sources, entirely new time-resolved scattering possibilities are opened. Synchrotron beams typically consist of sub-nanosecond pulses of x-rays separated in time by a few tens of nanoseconds to a few hundred nanoseconds so that these beams appear as continuous x-ray sources for investigations of phenomena on time scales ranging from hours down to microseconds. Studies requiring time-resolution ranging from microseconds to fractions of a nanosecond can be carried out in a triggering mode by stimulating the phenomena under investigation in coincidence with the x-ray pulses. Time resolution on the picosecond scale can, in principle, be achieved through the use of streak camera techniques in which the time structure of the individual x-ray pulses are viewed as quasi-continuous sources with ∼100--200 picoseconds duration. Techniques for carrying out time-resolved scattering measurements on time scales varying from picoseconds to kiloseconds at present and proposed synchrotron sources are discussed and examples of time-resolved studies are cited. 17 refs., 8 figs

  11. Time-resolved UV-IR pump-stimulated emission pump spectroscopy to probe collisional relaxation of $8p\\,^2P_{3/2}$ Cs I

    CERN Document Server

    Salahuddin, Mohammed; McFarland, Jacob; Bayram, S Burcin

    2015-01-01

    We describe and use a time-resolved pump-stimulated emission pump spectroscopic technique to measure collisional relaxation in a high-lying energy level of atomic cesium. Aligned $8p\\,^2P_{3/2}$ cesium atoms were produced by a pump laser. A second laser, the stimulated emission pump, promoted the population exclusively to the $5d\\,^2D_{5/2}$ level. The intensity of the $5d\\,^2D_{5/2}\\rightarrow6s\\,^2S_{1/2}$ cascade fluorescence at 852.12 nm was monitored. The linear polarization dependence of the $6s\\,^2S_{1/2}\\rightarrow8p\\,^2P_{3/2}\\rightarrow5d\\,^2S_{5/2}$ transition was measured in the presence of argon gas at various pressures. From the measurement, we obtained the disalignment cross section value for the $8p\\,^2P_{3/2}$ level due to collisions with ground-level argon atoms.

  12. Hyperfine structure and lifetime measurements in the 4s2nd 2D3/2 Rydberg sequence of Ga I by time-resolved laser spectroscopy

    Science.gov (United States)

    Liu, Chunqing; Tian, Yanshan; Yu, Qi; Bai, Wanshuang; Wang, Xinghao; Wang, Chong; Dai, Zhenwen

    2016-05-01

    The hyperfine structure (HFS) constants of the 4s2nd 2D3/2 (n=6-18) Rydberg sequence and the 4s26p 2P3/2 level for two isotopes of 69Ga and 71Ga atoms were measured by means of the time-resolved laser-induced fluorescence (TR-LIF) technique and the quantum beat method. The observed hyperfine quantum beat spectra were analyzed and the magnetic-dipole HFS constants A as well as the electric-quadrupole HFS constants B of these levels were obtained by Fourier transform and a program for multiple regression analysis. Also using TR-LIF method radiative lifetimes of the above sequence states were determined at room temperature. The measured lifetime values range from 69 to 2279 ns with uncertainties no more than 10%. To our knowledge, the HFS constants of this Rydberg sequence and the lifetimes of the 4s2nd 2D3/2 (n=10-18) levels are reported for the first time. Good agreement between our results and the previous is achieved.

  13. Time-resolved FTIR emission spectroscopy of Cu, Ag and Au in the 1300-4000 cm-1 region: transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr; Chernov, V. E.

    Poznań : Adam Mickiewicz University, 2010. s. 155. [International conference on high resolution molecular spectroscopy /21./. 07.09.2010-11.09.2010, Poznań] Institutional research plan: CEZ:AV0Z40400503 Keywords : FTIR spectroscopy * oscillator strengths Subject RIV: CF - Physical ; Theoretical Chemistry

  14. Optical technique for broadband microwave absorption spectroscopy in aqueous media

    International Nuclear Information System (INIS)

    Precise measurements of microwave absorption over a large range of frequencies in aqueous media are difficult to obtain and can result in conflicting results as a consequences of small differences in instrumentation. Traditional methods of microwave spectroscopy that make use of time-domain spectrometers or network analyzer systems provide only indirect measurement of the microwave absorption coefficient because they measure the real and imaginary parts of the dielectric constant, ε' and ε'', separately. The absorption coefficient must then be calculated from ε' and ε'' taking into account the geometry (e.g., of the waveguide and mode) among other factors. It has been shown that direct measurement of the microwave absorption coefficient α is possible using phase fluctuation optical heterodyne spectroscopy. Taking advantage of this hybrid optical-microwave technique the authors report on a broadband spectrometer with demonstrated accurate operation from 3 to 20 GHz

  15. Time-resolved quantitative phosphoproteomics

    DEFF Research Database (Denmark)

    Verano-Braga, Thiago; Schwämmle, Veit; Sylvester, Marc;

    2012-01-01

    proteins involved in the Ang-(1-7) signaling, we performed a mass spectrometry-based time-resolved quantitative phosphoproteome study of human aortic endothelial cells (HAEC) treated with Ang-(1-7). We identified 1288 unique phosphosites on 699 different proteins with 99% certainty of correct peptide...

  16. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase; Spectroscopie infrarouge resolue en temps pour l'etude de la dynamique femtoseconde du proton en phase liquide

    Energy Technology Data Exchange (ETDEWEB)

    Amir, W

    2003-12-15

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D{sub 2}O for reasons of experimental and theoretical suitability. However this is not water. Pure water H{sub 2}O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  17. A study of relaxation mechanisms in the A{sup 2}{Sigma}{sup +} state of nitric oxide by time resolved double resonant polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stampanoni-Panariello, A.; Bombach, R.; Hemmerling, B.; Hubschmid, W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Double resonant polarization labeling spectroscopy is applied to detect nitric oxide in flames and to characterize rotational energy transfer and orientation changing collisions in its first excited electronic state. (author) 4 figs., 3 refs.

  18. Investigation of uranium luminescence in SrB{sub 4}O{sub 7} matrix by time resolved photoluminescence, thermally stimulated luminescence and electron spin resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mohapatra, M.; Rajeswari, B.; Kadam, R.M.; Kumar, M.; Seshagiri, T.K.; Porwal, N.K.; Godbole, S.V.; Natarajan, V., E-mail: vnatra@barc.gov.in

    2014-10-25

    Highlights: • Optimization of U concentration for maximum PL yield and mechanism of quenching. • Identification of the two types of uranium species (UO{sub 6}{sup 6-}) present in the SBO matrix. • Evaluation of the TSL trap parameters and the order of the kinetics. • Formation of BOHC, BOEC and oxygen defect centers on gamma irradiation. • Proposition of a plausible mechanism for the observed photo and thermo luminescence. - Abstract: The luminescence of uranium in strontium borate (SrB{sub 4}O{sub 7}, SBO) matrix was investigated by time resolved photoluminescence, thermoluminescence (TSL) and electron spin resonance techniques (ESR). The samples were synthesized using solid state fusion reaction route and characterized by X-ray diffraction. Photoluminescence excitation and emission data suggested the stabilization of uranium as uranate (UO{sub 6}{sup 6-}) in the matrix. Luminescence decay time data suggested the stabilization of uranium at two different sites in the matrix. By giving suitable delay times and choosing proper gate widths, the two emission spectra due to the two uranate species could be obtained. Thermoluminescence investigation on the gamma-rays irradiated sample showed a strong glow peak at ∼415 K and a weak glow peak at 505 K. The dose response behavior, the trap parameters along with the order of kinetics for the strong glow peak were determined. To pinpoint the exact chemical nature of the defect centers responsible for the observed glow peaks, electron spin resonance technique was employed. Based on the ESR-TSL correlation data and the observed photoluminescence results, a plausible mechanism for the origin of the luminescence in the system was proposed.

  19. Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Shang-Chen; Putikam, Raghunath; Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw; Tsuchiya, Soji, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Nghia, N. T. [School of Chemical Engineering - Hanoi University of Science and Technology, Hanoi (Viet Nam); Nguyen, Hue M. T. [Center for Computational Science and Faculty of Chemistry, Hanoi National University of Education, Hanoi (Viet Nam); Lee, Yuan-Pern, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

    2014-10-21

    We investigated the reaction dynamics of O({sup 1}D) towards hydrogen atoms of two types in HCOOH. The reaction was initiated on irradiation of a flowing mixture of O{sub 3} and HCOOD or DCOOH at 248 nm. The relative vibration-rotational populations of OH and OD (1 ≦ v ≦ 4, J ≤ 15) states were determined from time-resolved IR emission recorded with a step-scan Fourier-transform spectrometer. In the reaction of O({sup 1}D) + HCOOD, the rotational distribution of product OH is nearly Boltzmann, whereas that of OD is bimodal. The product ratio [OH]/[OD] is 0.16 ± 0.05. In the reaction of O({sup 1}D) + DCOOH, the rotational distribution of product OH is bimodal, but the observed OD lines are too weak to provide reliable intensities. The three observed OH/OD channels agree with three major channels of production predicted with quantum-chemical calculations. In the case of O({sup 1}D) + HCOOD, two intermediates HOC(O)OD and HC(O)OOD are produced in the initial C−H and O−D insertion, respectively. The former undergoes further decomposition of the newly formed OH or the original OD, whereas the latter produces OD via direct decomposition. Decomposition of HOC(O)OD produced OH and OD with similar vibrational excitation, indicating efficient intramolecular vibrational relaxation, IVR. Decomposition of HC(O)OOD produced OD with greater rotational excitation. The predicted [OH]/[OD] ratio is 0.20 for O({sup 1}D) + HCOOD and 4.08 for O({sup 1}D) + DCOOH; the former agrees satisfactorily with experiments. We also observed the v{sub 3} emission from the product CO{sub 2}. This emission band is deconvoluted into two components corresponding to internal energies E = 317 and 96 kJ mol{sup −1} of CO{sub 2}, predicted to be produced via direct dehydration of HOC(O)OH and secondary decomposition of HC(O)O that was produced via decomposition of HC(O)OOH, respectively.

  20. Time-resolved Fourier-transform infrared emission spectroscopy of Au in the 1800-4000-cm(-1) region: Rydberg transitions

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav

    2010-01-01

    Roč. 81, č. 1 (2010), 012510. ISSN 1050-2947 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * Rydberg transitions * theoretical chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.861, year: 2010

  1. Time-resolved Fourier-transform infrared emission spectroscopy of Ag in the (1300-3600)-cm(-1) region: Transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr

    2010-01-01

    Roč. 82, č. 2 (2010), 022502. ISSN 1050-2947 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * transitions * oscillator strengths Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.861, year: 2010

  2. Time -resolved FTIR emission spectroscopy of Ag in the 1800-4000 cm-1 region: Transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Chernov, V. E.; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr

    Madrid: The Spanish Royal Society of Physics, 2010. -. [European Conference on Atoms Molecules and Photons /10./. 04.08.2010-09.08.2010, Salamanca] R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : FTIR spectroscopy * Au Subject RIV: CF - Physical ; Theoretical Chemistry

  3. Time-resolved FTIR emission spectroscopy of Cu in the 1800-3800 cm(-1) region: transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr; Kawaguchi, K.; Chernov, V. E.

    2011-01-01

    Roč. 44, č. 2 (2011), 025002. ISSN 0953-4075 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : metal poor stars * atomic data * FTIR emission spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.875, year: 2011

  4. Time-resolved molecular imaging

    Science.gov (United States)

    Xu, Junliang; Blaga, Cosmin I.; Agostini, Pierre; DiMauro, Louis F.

    2016-06-01

    Time-resolved molecular imaging is a frontier of ultrafast optical science and physical chemistry. In this article, we review present and future key spectroscopic and microscopic techniques for ultrafast imaging of molecular dynamics and show their differences and connections. The advent of femtosecond lasers and free electron x-ray lasers bring us closer to this goal, which eventually will extend our knowledge about molecular dynamics to the attosecond time domain.

  5. Continuous Vernier filtering of an optical frequency comb for broadband cavity-enhanced molecular spectroscopy

    CERN Document Server

    Rutkowski, Lucile

    2016-01-01

    We have recently introduced the Vernier-based Direct Frequency Comb Cavity-Enhanced Spectroscopy technique and we present the corresponding formalism for quantitative broadband spectroscopy. We achieve high sensitivity and broadband performance by acquiring spectra covering more than 2000 cm$^{-1}$ around 12600 cm$^{-1}$ (800 nm), resolving the 3$\

  6. Charge transport in TiO.sub.2./sub. films with complex percolation pathways investigated by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Zajac, Vít; Rychetský, Ivan; Fattakhova-Rohlfing, D.; Mandlmeier, B.; Bein, T.; Mics, Zoltan; Kužel, Petr

    2013-01-01

    Roč. 3, č. 3 (2013), s. 302-313. ISSN 2156-342X R&D Projects: GA ČR GAP204/12/0232; GA ČR GA13-12386S Grant ostatní: AVČR(CZ) M100101218 Institutional support: RVO:68378271 Keywords : terahertz spectroscopy * charge transport * TiO 2 nanoparticles Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.342, year: 2013

  7. Broadband ultrasonic spectroscopy for the characterization of viscoelastic materials.

    Science.gov (United States)

    Aksoy, Hüseyin Gökmen

    2016-04-01

    In this study, non-destructive experimental method based on acoustic through transmission technique along with broadband spectroscopy is proposed in order to determine the linear viscoelastic material properties in 20-400kHz range. Material properties such as phase velocity and attenuation coefficient of longitudinal and shear waves are measured. Diffraction correction developed for focused transducers is used to eliminate the spreading error due to the spherical wave generated by the hydrophone which is used as a transmitter. Method is validated on polymethyl methacrylate (PMMA). Both longitudinal wave velocity, shear wave velocity and attenuation coefficient of longitudinal wave of PMMA are in agreement with the previously reported values which are given in the literature. Attenuation coefficient of shear wave in PMMA is measured successfully and in agreement with the theoretical predictions. Longitudinal wave velocity and corresponding attenuation coefficient of gelatine gel are also measured. PMID:26859428

  8. Ultrafast free-carrier dynamics in Cu2ZnSnS4 single crystals studied using femtosecond time-resolved optical spectroscopy

    OpenAIRE

    Phuong, L. Q.; Okano, M; Yamada, Y.; Yamashita, G.; Morimoto, T.; Nagai, M.; Ashida, M; Nagaoka, A; Yoshino, K; Kanemitsu, Y.

    2014-01-01

    We studied the dynamics of photogenerated carriers in Cu2ZnSnS4 (CZTS) single crystals using femtosecond transient reflectivity (TR) and optical pump-THz probe transient absorption (THz-TA) spectroscopy. The TR and THz-TA decay dynamics consistently showed that free carriers have long lifetimes of up to a few nanoseconds. The excitation-photon-energy-dependent TR measurements revealed a slow picosecond energy relaxation of free carriers to the band edge in CZTS. The relaxation and recombinati...

  9. Development of time-resolved (e, 2e) electron momentum spectroscopy: a tool for visualizing the motion of electrons during a chemical reaction

    International Nuclear Information System (INIS)

    We report the instrumental design and technical details of an (e, 2e) electron momentum spectroscopy (EMS) apparatus, which employs an ultrashort-pulsed incident electron beam with a repetition rate of 5 kHz and a pulse duration in the order of one picosecond. EMS data for the neutral Ar atom in the ground state measured by using the pulsed electron beam are presented to illustrate the potential abilities of the apparatus for ultrafast molecular dynamics. The results are discussed mainly in terms of signal intensity

  10. Ultrafast free-carrier dynamics in Cu{sub 2}ZnSnS{sub 4} single crystals studied using femtosecond time-resolved optical spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Phuong, L. Q.; Kanemitsu, Y., E-mail: kanemitu@scl.kyoto-u.ac.jp [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan); Japan Science and Technology Agency, CREST, Uji, Kyoto 611-0011 (Japan); Okano, M.; Yamada, Y. [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan); Yamashita, G.; Morimoto, T.; Nagai, M.; Ashida, M. [Graduate School of Engineering Science, Osaka University, Osaka 560-8531 (Japan); Nagaoka, A. [Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501 (Japan); Department of Applied Physics and Electronic Engineering, University of Miyazaki, Miyazaki 889-2192 (Japan); Yoshino, K. [Department of Applied Physics and Electronic Engineering, University of Miyazaki, Miyazaki 889-2192 (Japan)

    2014-12-08

    We studied the dynamics of photogenerated carriers in Cu{sub 2}ZnSnS{sub 4} (CZTS) single crystals using femtosecond transient reflectivity (TR) and optical pump-THz probe transient absorption (THz-TA) spectroscopy. The TR and THz-TA decay dynamics consistently showed that free carriers have long lifetimes of up to a few nanoseconds. The excitation-photon-energy-dependent TR measurements revealed a slow picosecond energy relaxation of free carriers to the band edge in CZTS. The relaxation and recombination dynamics of free carriers were affected by nonradiative recombinations at the surface. Our results revealed a global feature of energy relaxation and recombination processes of free carriers in CZTS single crystals.

  11. Evaluation of superconducting gaps in optimally doped Ba(Fe1−xCox)2As2/Fe bilayers by ultrafast time-resolved spectroscopy

    International Nuclear Information System (INIS)

    Highlights: • Femtosecond spectroscopy measurements in FeSe0.5Te05 with Tc = 19 K are reported. • An estimation of a temperature-dependent energy gap Δ(T) at T < Tc is reported. • An electron–phonon constant λ = 06 is estimated. - Abstract: Measurements of nonequilibrium quasi-particle relaxation dynamics by using ultrafast pump and probe technique in optimally Co-doped Ba(Fe2As2)/Fe thin film has been reported. Multiple relaxation processes are present with BCS-like temperature-dependent superconducting gaps Δ0 = (3.67 ± 0.13) meV and Δ1 = (6.1 ± 0.1) meV, which are calculated considering the conventional electron-boson and spin fluctuations pairing mechanism. Then, the value of the electron–phonon coupling constant of λ = 0.18 has been obtained

  12. Time-resolved surface infrared spectroscopy during atomic layer deposition of TiO2 using tetrakis(dimethylamido)titanium and water

    International Nuclear Information System (INIS)

    Atomic layer deposition of titanium dioxide using tetrakis(dimethylamido)titanium (TDMAT) and water vapor is studied by reflection-absorption infrared spectroscopy (RAIRS) with a time resolution of 120 ms. At 190 °C and 240 °C, a decrease in the absorption from adsorbed TDMAT is observed without any evidence of an adsorbed product. Ex situ measurements indicate that this behavior is not associated with an increase in the impurity concentration or a dramatic change in the growth rate. A desorbing decomposition product is consistent with these observations. RAIRS also indicates that dehydroxylation of the growth surface occurs only among one type of surface hydroxyl groups. Molecular water is observed to remain on the surface and participates in reactions even at a relatively high temperature (110 °C) and with long purge times (30 s)

  13. Time-resolved surface infrared spectroscopy during atomic layer deposition of TiO{sub 2} using tetrakis(dimethylamido)titanium and water

    Energy Technology Data Exchange (ETDEWEB)

    Sperling, Brent A., E-mail: brent.sperling@nist.gov; Hoang, John; Kimes, William A.; Maslar, James E. [Chemical Sciences Division, National Institute of Standards and Technology, 100 Bureau Dr., Stop 8320, Gaithersburg, Maryland 20899-8320 (United States); Steffens, Kristen L. [Biomolecular Measurement Division, National Institute of Standards and Technology, 100 Bureau Dr., Stop 8362, Gaithersburg, Maryland 20899-8362 (United States); Nguyen, Nhan V. [Semiconductor and Dimensional Metrology Division, National Institute of Standards and Technology, 100 Bureau Dr., Stop 8120, Gaithersburg, Maryland 20899-8120 (United States)

    2014-05-15

    Atomic layer deposition of titanium dioxide using tetrakis(dimethylamido)titanium (TDMAT) and water vapor is studied by reflection-absorption infrared spectroscopy (RAIRS) with a time resolution of 120 ms. At 190 °C and 240 °C, a decrease in the absorption from adsorbed TDMAT is observed without any evidence of an adsorbed product. Ex situ measurements indicate that this behavior is not associated with an increase in the impurity concentration or a dramatic change in the growth rate. A desorbing decomposition product is consistent with these observations. RAIRS also indicates that dehydroxylation of the growth surface occurs only among one type of surface hydroxyl groups. Molecular water is observed to remain on the surface and participates in reactions even at a relatively high temperature (110 °C) and with long purge times (30 s)

  14. Changing Hydrogen-Bond Structure during an Aqueous Liquid-Liquid Transition Investigated with Time-Resolved and Two-Dimensional Vibrational Spectroscopy.

    Science.gov (United States)

    Bruijn, Jeroen R; van der Loop, Tibert H; Woutersen, Sander

    2016-03-01

    We investigate the putative liquid-liquid phase transition in aqueous glycerol solution, using the OD-stretch mode in dilute OD/OH isotopic mixtures to probe the hydrogen-bond structure. The conversion exhibits Avrami kinetics with an exponent of n = 2.9 ± 0.1 (as opposed to n = 1.7 observed upon inducing ice nucleation and growth in the same sample), which indicates a transition from one liquid phase to another. Two-dimensional infrared (2D-IR) spectroscopy shows that the initial and final phases have different hydrogen-bond structures: the former has a single Gaussian distribution of hydrogen-bond lengths, whereas the latter has a bimodal distribution consisting of a broad distribution and a narrower, ice-like distribution. The 2D-IR spectrum of the final phase is identical to that of ice/glycerol at the same temperature. Combined with the kinetic data this suggests that the liquid-liquid transformation is immediately followed by a rapid formation of small (probably nanometer-sized) ice crystals. PMID:26891098

  15. Time resolved spectroscopy and photometry of three little known bright cataclysmic variables: LS IV -08$^{\\rm o}$ 3, HQ Monocerotis and ST Chamaeleontis

    CERN Document Server

    Bruch, Albert

    2016-01-01

    As part of a project to better characterize comparatively bright but so far little studied cataclysmic variables in the southern hemisphere, we have obtained spectroscopic and photometric data of the nova-like variables LS IV -08$^{\\rm o}$ 3 and HQ Mon, and of the Z Cam type dwarf nova ST Cha. The spectra of all systems are as expected for their respective types. We derive improved orbital ephemeris of LS IV -08$^{\\rm o}$ 3 and map its accretion disk in the light of the H$\\alpha$ emission using Doppler tomography. We find that the emission has a two component origin, arising in the outer parts of the accretion disk and possibly on the illuminated face of the secondary star. The light curve of LS IV -08$^{\\rm o}$ 3 exhibits a low level of flickering and indications for a modulation on the orbital period. Spectroscopy of HQ Mon suggests an orbital period of $\\approx$5.15 hours which is incompatible with previous (uncertain) estimates. The light curves show the typical low scale flickering of UX UMa type nova-li...

  16. Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy.

    Science.gov (United States)

    Samjeské, Gabor; Miki, Atsushi; Ye, Shen; Osawa, Masatoshi

    2006-08-24

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account. PMID:16913790

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-08-01

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

  18. Femtosecond time-resolved laser-induced breakdown spectroscopy for detection and identification of bacteria: A comparison to the nanosecond regime

    Science.gov (United States)

    Baudelet, Matthieu; Guyon, Laurent; Yu, Jin; Wolf, Jean-Pierre; Amodeo, Tanguy; Fréjafon, Emeric; Laloi, Patrick

    2006-04-01

    Bacterial samples (Escherichia coli and Bacillus subtilis) have been analyzed by laser-induced breakdown spectroscopy (LIBS) using femtosecond pulses. We compare the obtained spectra with those resulting from the classical nanosecond LIBS. Specific features of femtosecond LIBS have been demonstrated, very attractive for analyzing biological sample: (i) a lower plasma temperature leading to negligible nitrogen and oxygen emissions from excited ambient air and a better contrast in detection of trace mineral species; and (ii) a specific ablation regime that favors intramolecular bonds emission with respect to atomic emission. A precise kinetic study of molecular band head intensities allows distinguishing the contribution of native CN bonds released by the sample from that due to carbon recombination with atmospheric nitrogen. Furthermore a sensitive detection of trace mineral elements provide specific spectral signature of different bacteria. An example is given for the Gram test provided by different magnesium emissions from Escherichia coli and Bacillus subtilis. An entire spectrum consists of hundred resolved lines belonging to 13 atomic or molecular species, which provides an ensemble of valuable data to identify different bacteria.

  19. Probing of the local environment and calculation of J.O. parameters for Eu{sup 3+} CMPO functionalized pillararene complexes by time resolved fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Arijit, E-mail: arijita@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Fang, Yuyu; Yuan, Xiangyang; Yuan, Lihua [Key Laboratory for Radiation Physics and Technology of Ministry of Education, Institute of Nuclear Science and Technology, College of Chemistry, Sichuan University, Chengdu 610064 (China)

    2015-10-15

    An attempt was made to understand the complexation of Eu{sup 3+} with structurally modified CMPO-functionalized pillararenes by luminescence spectroscopy. Formation of single species with different numbers of inner sphere water molecules was found to be present for all the complexes. On increasing spacer length between ligating moieties and supramolecular pillararenes, the stereo-chemical crowding around ligating oxygen decreased. Therefore, strong covalent metal–oxygen bond was formed which was reflected in the increasing trend of the computed Ω{sub 2} values (Judd–Offelt parameter): LI (4.66×10{sup −20})LII (3.19 ms)>LIII (2.94 ms) while the branching ratio values for all three complexes followed the same trend as β{sub 2}>β{sub 4}>β{sub 1}. The other photo-physical constants like asymmetric factor, quantum efficiency, magnetic and electric dipole transition probabilities were also computed. - Highlights: • Probing of the local environment of Eu{sup 3+} complex with three structurally modified CMPO functionalized pillararenes. • J.O. parameter Ω{sub 2} followed the trend: LI (4.66E−20)

  20. Development of a single-shot CCD-based data acquisition system for time-resolved X-ray photoelectron spectroscopy at an X-ray free-electron laser facility

    International Nuclear Information System (INIS)

    A single-shot CCD-based data acquisition system for time-resolved photoelectron spectroscopy using an X-ray free-electron laser has been developed. The basic performance of the system is demonstrated using XFEL-induced and synchrotron-radiation-induced Ti 1s core-level spectroscopy. In order to utilize high-brilliance photon sources, such as X-ray free-electron lasers (XFELs), for advanced time-resolved photoelectron spectroscopy (TR-PES), a single-shot CCD-based data acquisition system combined with a high-resolution hemispherical electron energy analyzer has been developed. The system’s design enables it to be controlled by an external trigger signal for single-shot pump–probe-type TR-PES. The basic performance of the system is demonstrated with an offline test, followed by online core-level photoelectron and Auger electron spectroscopy in ‘single-shot image’, ‘shot-to-shot image (image-to-image storage or block storage)’ and ‘shot-to-shot sweep’ modes at soft X-ray undulator beamline BL17SU of SPring-8. In the offline test the typical repetition rate for image-to-image storage mode has been confirmed to be about 15 Hz using a conventional pulse-generator. The function for correcting the shot-to-shot intensity fluctuations of the exciting photon beam, an important requirement for the TR-PES experiments at FEL sources, has been successfully tested at BL17SU by measuring Au 4f photoelectrons with intentionally controlled photon flux. The system has also been applied to hard X-ray PES (HAXPES) in ‘ordinary sweep’ mode as well as shot-to-shot image mode at the 27 m-long undulator beamline BL19LXU of SPring-8 and also at the SACLA XFEL facility. The XFEL-induced Ti 1s core-level spectrum of La-doped SrTiO3 is reported as a function of incident power density. The Ti 1s core-level spectrum obtained at low power density is consistent with the spectrum obtained using the synchrotron source. At high power densities the Ti 1s core-level spectra show

  1. Development of a single-shot CCD-based data acquisition system for time-resolved X-ray photoelectron spectroscopy at an X-ray free-electron laser facility

    Energy Technology Data Exchange (ETDEWEB)

    Oura, Masaki, E-mail: oura@spring8.or.jp; Wagai, Tatsuya; Chainani, Ashish [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Miyawaki, Jun [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); The University of Tokyo, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Sato, Hiromi [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Matsunami, Masaharu [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); The University of Tokyo, Kashiwanoha 5-1-5, Kashiwa, Chiba 277-8581 (Japan); Institute for Molecular Science, Myodaiji, Okazaki, Aichi 444-8585 (Japan); Eguchi, Ritsuko [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); The University of Tokyo, Kashiwanoha 5-1-5, Kashiwa, Chiba 277-8581 (Japan); Okayama University, Okayama 700-8530 (Japan); Kiss, Takayuki; Yamaguchi, Takashi; Nakatani, Yasuhiro [Osaka University, Toyonaka, Osaka 560-8531 (Japan); Togashi, Tadashi; Katayama, Tetsuo [JASRI, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Ogawa, Kanade; Yabashi, Makina; Tanaka, Yoshihito; Kohmura, Yoshiki; Tamasaku, Kenji [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Shin, Shik [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); The University of Tokyo, Kashiwanoha 5-1-5, Kashiwa, Chiba 277-8581 (Japan); Ishikawa, Tetsuya [RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2013-12-10

    A single-shot CCD-based data acquisition system for time-resolved photoelectron spectroscopy using an X-ray free-electron laser has been developed. The basic performance of the system is demonstrated using XFEL-induced and synchrotron-radiation-induced Ti 1s core-level spectroscopy. In order to utilize high-brilliance photon sources, such as X-ray free-electron lasers (XFELs), for advanced time-resolved photoelectron spectroscopy (TR-PES), a single-shot CCD-based data acquisition system combined with a high-resolution hemispherical electron energy analyzer has been developed. The system’s design enables it to be controlled by an external trigger signal for single-shot pump–probe-type TR-PES. The basic performance of the system is demonstrated with an offline test, followed by online core-level photoelectron and Auger electron spectroscopy in ‘single-shot image’, ‘shot-to-shot image (image-to-image storage or block storage)’ and ‘shot-to-shot sweep’ modes at soft X-ray undulator beamline BL17SU of SPring-8. In the offline test the typical repetition rate for image-to-image storage mode has been confirmed to be about 15 Hz using a conventional pulse-generator. The function for correcting the shot-to-shot intensity fluctuations of the exciting photon beam, an important requirement for the TR-PES experiments at FEL sources, has been successfully tested at BL17SU by measuring Au 4f photoelectrons with intentionally controlled photon flux. The system has also been applied to hard X-ray PES (HAXPES) in ‘ordinary sweep’ mode as well as shot-to-shot image mode at the 27 m-long undulator beamline BL19LXU of SPring-8 and also at the SACLA XFEL facility. The XFEL-induced Ti 1s core-level spectrum of La-doped SrTiO{sub 3} is reported as a function of incident power density. The Ti 1s core-level spectrum obtained at low power density is consistent with the spectrum obtained using the synchrotron source. At high power densities the Ti 1s core-level spectra

  2. Time resolved spectroscopic studies on some nanophosphors

    Indian Academy of Sciences (India)

    Harish Chander; Santa Chawla

    2008-06-01

    Time resolved spectroscopy is an important tool for studying photophysical processes in phosphors. Present work investigates the steady state and time resolved photoluminescence (PL) spectroscopic characteristics of ZnS, ZnO and (Zn, Mg)O nanophosphors both in powder as well as thin film form. Photoluminescence (PL) of ZnS nanophosphors typically exhibit a purple/blue emission peak termed as self activated (SA) luminescence and emission at different wavelengths arising due to dopant impurities e.g. green emission for ZnS : Cu, orange emission for ZnS : Mn and red emission for ZnS : Eu. The lifetimes obtained from decay curves range from ns to ms level and suggest the radiative recombination path involving donor–acceptor pair recombination or internal electronic transitions of the impurity atom. A series of ZnMgO nanophosphor thin films with varied Zn : Mg ratios were prepared by chemical bath deposition. Photoluminescence (PL) excitation and emission spectra exhibit variations with changing Mg ratio. Luminescence lifetime as short as 10-10 s was observed for ZnO and ZnMgO (100 : 10) nanophosphors. With increasing Mg ratio, PL decay shifts into microsecond range. ZnO and ZnMgO alloys up to 50% Mg were prepared as powder by solid state mixing and sintering at high temperature in reducing atmosphere. Time resolved decay of PL indicated lifetime in the microsecond time scale. The novelty of the work lies in clear experimental evidence of dopants (Cu, Mn, Eu and Mg) in the decay process and luminescence life times in II–VI semiconductor nanocrystals of ZnS and ZnO. For ZnS, blue self activated luminescence decays faster than Cu and Mn related emission. For undoped ZnO nanocrystals, PL decay is in the nanosecond range whereas with Mg doping the decay becomes much slower in the microsecond range.

  3. Near-field imaging and nano-Fourier-transform infrared spectroscopy using broadband synchrotron radiation.

    Science.gov (United States)

    Hermann, Peter; Hoehl, Arne; Patoka, Piotr; Huth, Florian; Rühl, Eckart; Ulm, Gerhard

    2013-02-11

    We demonstrate scanning near-field optical microscopy with a spatial resolution below 100 nm by using low intensity broadband synchrotron radiation in the IR regime. The use of such a broadband radiation source opens up the possibility to perform nano-Fourier-transform infrared spectroscopy over a wide spectral range. PMID:23481749

  4. Time-resolved diffused optical characterization of key tissue constituents of human bony prominence locations

    Science.gov (United States)

    Konugolu Venkata Sekar, Sanathana; Farina, Andrea; Martinenghi, Edoardo; Dalla Mora, Alberto; Taroni, Paola; Pifferi, Antonio; Negredo, Eugènia; Puig, Jordi; Escrig, Roser; Rosales, Quim; Lindner, Claus; Pagliazzi, Marco; Durduran, Turgut

    2015-07-01

    We report a broadband time-resolved characterization of selected bony prominence locations of the human body. A clinical study was performed at six different bony prominence locations of 53 subjects. A portable broadband time-resolved system equipped with pulse drift and distortion compensation strategy was used for absorption and scattering measurements. Key tissue constituents were quantified as a pilot step towards non-invasive optical assessment of bone pathologies.

  5. Time-resolved spectroscopy using synchrotron radiation

    International Nuclear Information System (INIS)

    Work performed at the Stanford Synchrotron Radiation Laboratory (SSRL) is reported. The timing characteristics of the SPEAR beam (pulse width less than or equal to 0.4 nsec, pulse repetition period = 780 nsec) were exploited to determine dynamic behavior of atomic, molecular, excimeric, and photodissociative gas-phase species excited by vacuum-ultraviolet (VUV) radiation. Fast fluorescence timing measurements were done to determine excited-state lifetimes of Kr and Xe. Pressure-dependent timing studies on Xe gas at higher concentrations demonstrated some of the problems associated with previous kinetic modeling of the Xe2 system. It was found that even qualitative agreement of observed Xe2 lifetimes as a function of pressure required the assumption that the radiative lifetime was a strong function of internuclear separation. The radiative decays of chemically unstable fragments, CN* (B2Σ+) and XeF* (B2Σ+ and C2 Pi/sub 3/2//), were studied by pulsed photodissociation of stable parent compounds, ICN and XeF2. When the polarization of the CN* (B2Σ+) fragment fluorescence was measured, it was found to be non-zero and strongly dependent on excitation wavelength. This polarization is related to the symmetry of the photodissociative surface via a classical model, and the variations in the polarization with wavelength is attributed to symmetry and lifetime effects of a predissociating parent molecule. Despite the drawbacks of limited availability and low radiation flux, synchrotron radiation is definitely a useful spectroscopic tool for VUV studies of gas-phase systems

  6. Optimal multisine excitation design for broadband electrical impedance spectroscopy

    International Nuclear Information System (INIS)

    Electrical impedance spectroscopy (EIS) can be used to characterize biological materials in applications ranging from cell culture to body composition, including tissue and organ state. The emergence of cell therapy and tissue engineering opens up a new and promising field of application. While in most cases classical measurement techniques based on a frequency sweep can be used, EIS based on broadband excitations enables dynamic biological systems to be characterized when the measuring time and injected energy are a constraint. Myocardial regeneration, cell characterization in micro-fluidic systems and dynamic electrical impedance tomography are all examples of such applications. The weakness of such types of fast EIS measuring techniques resides in their intrinsic loss of accuracy. However, since most of the practical applications have no restriction over the excitation used, the input power spectrum can be appropriately designed to maximize the accuracy obtained from the measurements. This paper deals with the problem of designing the optimal multisine excitation for electrical bioimpedance measurements. The optimal multisine is obtained by the minimization of the Cramer–Rao lower bound, or what is the same, by maximizing the accuracy obtained from the measurements. Furthermore, because no analytical solution exists for global optimization involving time and frequency domains jointly, this paper presents the multisine optimization approach partially in both domains and then combines the results. As regards the frequency domain approach, a novel contribution is made for the multisine amplitude power spectrum. In the time domain, multisine is optimized by reducing its crest factor. Moreover, the impact on the information and accuracy of the impedance spectrum obtained from using different multisine amplitude power spectra is discussed, as well as the number of frequencies and frequency distributions. The theory is supported by a set of validation measurements

  7. Optimal multisine excitation design for broadband electrical impedance spectroscopy

    Science.gov (United States)

    Sanchez, B.; Vandersteen, G.; Bragos, R.; Schoukens, J.

    2011-11-01

    Electrical impedance spectroscopy (EIS) can be used to characterize biological materials in applications ranging from cell culture to body composition, including tissue and organ state. The emergence of cell therapy and tissue engineering opens up a new and promising field of application. While in most cases classical measurement techniques based on a frequency sweep can be used, EIS based on broadband excitations enables dynamic biological systems to be characterized when the measuring time and injected energy are a constraint. Myocardial regeneration, cell characterization in micro-fluidic systems and dynamic electrical impedance tomography are all examples of such applications. The weakness of such types of fast EIS measuring techniques resides in their intrinsic loss of accuracy. However, since most of the practical applications have no restriction over the excitation used, the input power spectrum can be appropriately designed to maximize the accuracy obtained from the measurements. This paper deals with the problem of designing the optimal multisine excitation for electrical bioimpedance measurements. The optimal multisine is obtained by the minimization of the Cramer-Rao lower bound, or what is the same, by maximizing the accuracy obtained from the measurements. Furthermore, because no analytical solution exists for global optimization involving time and frequency domains jointly, this paper presents the multisine optimization approach partially in both domains and then combines the results. As regards the frequency domain approach, a novel contribution is made for the multisine amplitude power spectrum. In the time domain, multisine is optimized by reducing its crest factor. Moreover, the impact on the information and accuracy of the impedance spectrum obtained from using different multisine amplitude power spectra is discussed, as well as the number of frequencies and frequency distributions. The theory is supported by a set of validation measurements when

  8. Structural and dynamical properties of Mg65Cu25Y10 metallic glasses studied by in situ high energy X-ray diffraction and time resolved X-ray photon correlation spectroscopy

    International Nuclear Information System (INIS)

    Highlights: • Study of rapidly quenched Mg-based metallic glasses under different thermal paths. • The atomic dynamics was investigated by X-ray photon correlation spectroscopy. • The structural changes were followed by in situ high energy X-ray diffraction. • Dynamical and structural properties of Mg-based metallic glasses at the atomic level. • Strengthened idea of a stress-induced atomic motion in metallic glasses. - Abstract: We present a temperature investigation of the structural and dynamical evolution of rapidly quenched metallic glasses of Mg65Cu25Y10 at the atomic length scale by means of in situ high energy X-ray diffraction and time resolved X-ray photon correlation spectroscopy. We find a flattening of the temperature evolution of the position of the first sharp diffraction peak on approaching the glass transition temperature from the glassy state, which reflects into a surprising slowing down of the relaxation dynamics of even one order of magnitude with increasing temperature. The comparison between structural and dynamical properties strengthens the idea of a stress-induced, rather than pure diffusive, atomic motion in metallic glasses

  9. Sensing cell metabolism by time-resolved autofluorescence

    Science.gov (United States)

    Wu, Yicong; Zheng, Wei; Qu, Jianan Y.

    2006-11-01

    We built a time-resolved confocal fluorescence spectroscopy system equipped with the multichannel time-correlated single-photon-counting technique. The instrument provides a unique approach to study the fluorescence sensing of cell metabolism via analysis of the wavelength- and time-resolved intracellular autofluorescence. The experiments on monolayered cell cultures show that with UV excitation at 365 nm the time-resolved autofluorescence decays, dominated by free-bound reduced nicotinamide adenine dinucleotide signals, are sensitive indicators for cell metabolism. However, the sensitivity decreases with the increase of excitation wavelength possibly due to the interference from free-bound flavin adenine dinucleotide fluorescence. The results demonstrate that time-resolved autofluorescence can be potentially used as an important contrast mechanism to detect epithelial precancer.

  10. Broadband spectroscopy of slow dynamics in glass transition

    Science.gov (United States)

    Park, In-Sung

    The purpose of this study is to clarify the slow dynamics of the intermediate liquid by dielectric and calorimetric method. Although alcohols has a simple molecular structure, it shows the non-Debye type relaxation and the existence of several relaxation modes due to the hydrogen bonding. Dielectric relaxation was studied by the broadband dielectric spectroscopy using impedance analyzer and time domain reflectometry (TDR) technique. It covers the frequency range of 10 mHz to 10 GHz. Calorimetric measurement was carried out using the modulated differential scanning calorimetry (MDSC). The complex dielectric permittivity and complex heat capacity of several alcohols were measured in the liquid, supercooled liquid and glass states. The roles of hydrogen bonding and molecular structure in the relaxation feature are discussed in respect to the number of -OH group, the bonded position of the -OH group to alkyl group, its substitution by heavy deuterium and -OCH 3 group, and the molecular weights. All samples studied show several universal features, (1)The relaxation behavior has a crossover near the melting point, (2)The dielectric strength of the main relaxation mode can be well described by the modified Onsager equation, and (3)The beta parameter in Kohlrausch-Williams-Watts function is a monotonically increasing function of temperature. The relaxation behavior of alcohol was explained in terms of the frustration between the density and bond order parameters on the basis of the two order parameter model. Both the Adam-Gibbs theory and Matsuoka's domain model derived the Vogel-Tammann-Fulcher relation for the thermal and dielectric behaviors. The correlation between calorimetric and dielectric measurements supports the fact that the dielectric relaxation behavior originates from the structural change during the liquid-glass transition. The minimum configurational entropy and domain size are quantitatively determined for the propylene glycol monomer and its oligomers.

  11. Uptake Of Trivalent Actinides (Cm(III)) And Lanthanides (Eu(III)) By Cement-Type Minerals: A Wet Chemistry And Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) Study

    Energy Technology Data Exchange (ETDEWEB)

    Tits, J.; Stumpf, T; Wieland, E.; Fanghaenel, T

    2003-03-01

    The interaction of the two chemical homologues Cm (III) and Eu(III) with calcium silicate hydrates at pH 13.3 has been investigated in batch-type sorption studies using Eu(III), and complemented with time-resolved laser fluorescence spectroscopy using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics, and a strong uptake by CSH phases, with distribution ratios of 6({+-}3)*105 L kg-1. Three different types of sorbed Cm(III) species have been identified: a non-fluorescing species, which was identified as Cm cluster present either as surface precipitate or as Cm(III) colloid in solution, and two sorbed fluorescing species. The sorbed fluorescing species have characteristic emission spectra (main peak maxima at 618.9 nm and 620.9 nm) and fluorescence emission lifetimes (289 {+-} 11 ms and 1482{+-} 200 ms). From the fluorescence lifetimes, it appears that the two fluorescing Cm(III) species have, respectively, one to two or no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution of Ca at two different types of sites in the CSH structure. (author)

  12. Optical characterization of fourfold (T{sub d})- and sixfold (O{sub h})-transition-metal species in MgAl{sub 2}O{sub 4}:Co{sup 2+} by time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nataf, L., E-mail: lucie.nataf@unican.e [DCITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Rodriguez, F. [DCITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Valiente, R. [Department Fisica Aplicada, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Ulanov, V. [Russian Academy of Sciences, Sibirski Trakt 10/7, 420029 Kazan (Russian Federation)

    2009-12-15

    This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl{sub 2}O{sub 4}:Co{sup 2+}. Besides the well-known fourfold-coordinated Co{sup 2+}(T{sub d}) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr{sup 3+}(O{sub h}) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co{sup 2+}(T{sub d}) emission at 670 nm varies from tau=6.7 mus to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T{sub d} systems is related to the excited-state crossover ({sup 4}T{sub 1}reversible{sup 2}E), making the emission band to transform from a narrow-like emission from {sup 2}E at low temperature to a broad structureless band from {sup 4}T{sub 1} at room temperature.

  13. Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.;

    1996-01-01

    The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics was...... studied with SF6 pressures of 5-1000 mbar at 298 K. Comparative studies were carried out by monitoring the decay kinetics of NO2 at 445 nm using pressures of 100-1000 mbar at 295 and 341 K. The observed pressure dependence is represented in terms of a fall-off curve with the following values of the...... limiting high- and low-pressure rate coefficients, k(rec,proportional to) = (2.1 +/- 1.0)x 10(10) (T/300)(0.5) M(-1) s(-1) and K-rec,K-0/[SF6] = (3.8 +/- 1.8) x 10(12) (T/300)(-24) M(-2) S-1 in the temperature rang 200-400 K, and with a broadening factor, F-cent = 0.587X (T/300>(-0.32)....

  14. High-sensitivity broadband microwave spectroscopy with small nonresonant coils

    Science.gov (United States)

    Mahdjour, H.; Clark, W. G.; Baberschke, K.

    1986-06-01

    The use of a small, nonresonant, coil of micron dimensions as the microwave magnetic field structure of a broadband electron-spin-resonance (ESR) spectrometer is described. The coil is driven by a broadband microwave generator which operates between 0.1 and 8.5 GHz. The samples may fill the coil to approximately 100 percent. It is shown that for small size samples this system offers higher sensitivity than a conventional cavity spectrometer. Because the system is broadband, either frequency scans or the conventional magnetic field scans can be used to traverse the resonance. Examples for DPPH and for the spin glass AgMn using this method are reported. Since the sample coil is small, it has many potential applications, such as insertion into the mixing chamber of dilution refrigerator or high-pressure cell, efficient use of power in ENDOR and other double resonance experiments, and rapid recovery from transients in pulsed ESR experiments.

  15. Broadband cavity enhanced spectroscopy in the ultraviolet spectral region for measurements of nitrogen dioxide and formaldehyde

    OpenAIRE

    Washenfelder, R. A.; A. R. Attwood; Flores, J. M.; Rudich, Y.; S. S. Brown

    2015-01-01

    Formaldehyde (CH2O) is the most abundant aldehyde in the atmosphere, and strongly affects photochemistry through its photolysis. We describe simultaneous measurements of CH2O and nitrogen dioxide (NO2) using broadband cavity enhanced spectroscopy in the ultraviolet spectral region. The light source consists of a continuous-wave diode laser focused into a Xenon bulb to produce a plasma that emits high-intensity, broadband light. The plasma discharge is optically filtered and ...

  16. Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) – applicability and corrections

    OpenAIRE

    U. Platt; J. Meinen; D. Pöhler; T. Leisner

    2008-01-01

    Atmospheric trace gas measurements by cavity assisted long-path absorption spectroscopy are an emerging technology. An interesting approach is the combination of CEAS with broadband light sources, the broadband CEAS (BB-CEAS). BB-CEAS lends itself to the application of the DOAS technique to analyse the derived absorption spectra. While the DOAS approach has enormous advantages in terms of sensitivity and specificity of the measurement, an important implication is the reduction of the light pa...

  17. Development of a single-shot CCD-based data acquisition system for time-resolved X-ray photoelectron spectroscopy at an X-ray free-electron laser facility.

    Science.gov (United States)

    Oura, Masaki; Wagai, Tatsuya; Chainani, Ashish; Miyawaki, Jun; Sato, Hiromi; Matsunami, Masaharu; Eguchi, Ritsuko; Kiss, Takayuki; Yamaguchi, Takashi; Nakatani, Yasuhiro; Togashi, Tadashi; Katayama, Tetsuo; Ogawa, Kanade; Yabashi, Makina; Tanaka, Yoshihito; Kohmura, Yoshiki; Tamasaku, Kenji; Shin, Shik; Ishikawa, Tetsuya

    2014-01-01

    In order to utilize high-brilliance photon sources, such as X-ray free-electron lasers (XFELs), for advanced time-resolved photoelectron spectroscopy (TR-PES), a single-shot CCD-based data acquisition system combined with a high-resolution hemispherical electron energy analyzer has been developed. The system's design enables it to be controlled by an external trigger signal for single-shot pump-probe-type TR-PES. The basic performance of the system is demonstrated with an offline test, followed by online core-level photoelectron and Auger electron spectroscopy in 'single-shot image', 'shot-to-shot image (image-to-image storage or block storage)' and `shot-to-shot sweep' modes at soft X-ray undulator beamline BL17SU of SPring-8. In the offline test the typical repetition rate for image-to-image storage mode has been confirmed to be about 15 Hz using a conventional pulse-generator. The function for correcting the shot-to-shot intensity fluctuations of the exciting photon beam, an important requirement for the TR-PES experiments at FEL sources, has been successfully tested at BL17SU by measuring Au 4f photoelectrons with intentionally controlled photon flux. The system has also been applied to hard X-ray PES (HAXPES) in `ordinary sweep' mode as well as shot-to-shot image mode at the 27 m-long undulator beamline BL19LXU of SPring-8 and also at the SACLA XFEL facility. The XFEL-induced Ti 1s core-level spectrum of La-doped SrTiO3 is reported as a function of incident power density. The Ti 1s core-level spectrum obtained at low power density is consistent with the spectrum obtained using the synchrotron source. At high power densities the Ti 1s core-level spectra show space-charge effects which are analysed using a known mean-field model for ultrafast electron packet propagation. The results successfully confirm the capability of the present data acquisition system for carrying out the core-level HAXPES studies of condensed matter induced by the XFEL. PMID:24365935

  18. Multicomponent gas analysis using broadband quantum cascade laser spectroscopy

    OpenAIRE

    Reyes Reyes, A.; Hou, Z.; Van Mastrigt, E.; Horsten, R.C.; J. C. De Jongste; Pijnenburg, M. W.; Urbach, H.P.; Bhattacharya, N.

    2014-01-01

    We present a broadband quantum cascade laser-based spectroscopic system covering the region between 850 and 1250 cm−1. Its robust multipass cavity ensures a constant interaction length over the entire spectral region. The device enables the detection and identification of numerous molecules present in a complex gas mixture without any pre-treatment in two minutes. We demonstrate that we can detect sub-ppmv concentration of acetone in presence of 2% of water at the same wavenumber region.

  19. Multicomponent gas analysis using broadband quantum cascade laser spectroscopy.

    Science.gov (United States)

    Reyes-Reyes, A; Hou, Z; van Mastrigt, E; Horsten, R C; de Jongste, J C; Pijnenburg, M W; Urbach, H P; Bhattacharya, N

    2014-07-28

    We present a broadband quantum cascade laser-based spectroscopic system covering the region between 850 and 1250 cm(-1). Its robust multipass cavity ensures a constant interaction length over the entire spectral region. The device enables the detection and identification of numerous molecules present in a complex gas mixture without any pre-treatment in two minutes. We demonstrate that we can detect sub-ppmv concentration of acetone in presence of 2% of water at the same wavenumber region. PMID:25089450

  20. Self-referenced ultra-broadband transient terahertz spectroscopy using air-photonics.

    Science.gov (United States)

    D'Angelo, F; Němec, H; Parekh, S H; Kužel, P; Bonn, M; Turchinovich, D

    2016-05-01

    Terahertz (THz) air-photonics employs nonlinear interactions of ultrashort laser pulses in air to generate and detect THz pulses. As air is virtually non-dispersive, the optical-THz phase matching condition is automatically met, thus permitting the generation and detection of ultra-broadband THz pulses covering the entire THz spectral range without any gaps. Air-photonics naturally offers unique opportunities for ultra-broadband transient THz spectroscopy, yet many critical challenges inherent to this technique must first be resolved. Here, we present explicit guidelines for ultra-broadband transient THz spectroscopy with air-photonics, including a novel method for self-referenced signal acquisition minimizing the phase error, and the numerically-accurate approach to the transient reflectance data analysis. PMID:27137624

  1. Completely background free broadband coherent anti-Stokes Raman scattering spectroscopy

    DEFF Research Database (Denmark)

    Liu, Xing; Niu, Hanben; Liu, Wei; Chen, Danni; Zhou, Binbin; Bache, Morten

    2013-01-01

    For the first time it was proposed a numerical approach to obtain non-NRB time-frequency coherent anti-Stokes Raman scattering (CARS) spectrograms. In order to evaluate the validity of the CARS spectrogram for background free broadband CARS spectroscopy, the authors numerically constructed a CARS...

  2. Broadband sample holder for microwave spectroscopy of superconducting qubits

    International Nuclear Information System (INIS)

    We present a practical design and implementation of a broadband sample holder suitable for microwave experiments with superconducting integrated circuits at millikelvin temperatures. Proposed design can be easily integrated in standard dilution cryostats, has flat pass band response in a frequency range from 0 to 32 GHz, allowing the RF testing of the samples with substrate size up to 4 × 4 mm2. The parasitic higher modes interference in the holder structure is analyzed and prevented via design considerations. The developed setup can be used for characterization of superconducting parametric amplifiers, bolometers, and qubits. We tested the designed sample holder by characterizing of a superconducting flux qubit at 20 mK temperature

  3. Optomechanical spectroscopy with broadband interferometric and quantum cascade laser sources

    Energy Technology Data Exchange (ETDEWEB)

    Tetard, Laurene [ORNL; Passian, Ali [ORNL; Farahi, R H [ORNL; Davison, Brian H [ORNL; Thundat, Thomas George [ORNL

    2011-01-01

    The spectral tunability of semiconductor-metal multilayer structures can provide a channel for the conversion of light into useful mechanical actuation. Response of suspended silicon, silicon nitride, chromium, gold, and aluminum microstructures is shown to be utilized as a detector for visible and infrared spectroscopy. Both dispersive and interferometric approaches are investigated to delineate the potential use of the structures in spatially resolved spectroscopy and spectrally resolved microscopy. The thermoplasmonic, spectral absorption, interference effects, and the associated energy deposition that contributes to the mechanical response are discussed to describe the optomechanical detection to be of potential importance in future integrated spectrometers.

  4. Study of the interaction of trivalent actinide and lanthanide ions with human serum transferrin by means of time-resolved laser-fluorescence spectroscopy; Untersuchung der Wechselwirkung trivalenter Actinid- und Lanthanidionen mit humanem Serumtransferrin mittels zeitaufgeloester Laserfluoreszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Nicole

    2015-04-27

    In the present work the complexation of Cm(III), Eu(III) and Am(III) with human serum transferrin is studied. The aim of this work was the identification and the spectroscopic and thermodynamic characterization of An(III) and Ln(III) transferrin complex species. Different speciation methods, such as time-resolved laser fluorescence spectroscopy (TRLFS), luminescence spectroscopy and EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy were applied. Using TRLFS two unambiguously different Cm(III) transferrin species were identified for the first time. In the pH range from 3.5 to 9.7 the Cm(III) transferrin species I is formed revealing complexation of the metal ion at a nonspecific site of the protein surface. In case of the Cm(III) transferrin species II Cm(III) is bound at the Fe(III) binding site of the protein resulting in a 4-fold coordination via amino acid groups of the protein (His, Asp, 2 x Tyr) and coordination of two water molecules and three additional ligands, e.g. OH{sup -} or CO{sub 3}{sup 2-}. Due to the kinetic and thermodynamic differences of the binding sites of the N- and C-lobe, the experimental conditions ensure exclusive coordination of Cm(III) at the C-terminal binding site. In addition to the complexation studies of Cm(III) with transferrin, the interaction with the recombinant N-lobe of human serum transferrin (hTf/2N) as a model component for the transferrin N-lobe was investigated. At pH≥7.4 a Cm(III) hTf/2N species with Cm(III) bound at the Fe(III) binding site is formed which is comparable to the Cm(III) transferrin species II. An increase of the temperature from room temperature (T=296 K) to physiological temperature (T=310 K) favors the complexation of Cm(III) with both transferrin and hTf/2N. The complexation of Cm(III) with transferrin was investigated at three different carbonate concentrations (c(carbonate){sub tot}=0 mM, 0,23 mM und 25 mM (physiological carbonate concentration)). An increase of the total carbonate

  5. Decomposition of time-resolved tomographic PIV

    NARCIS (Netherlands)

    Schmid, P.J.; Violato, D.; Scarano, F.

    2012-01-01

    An experimental study has been conducted on a transitional water jet at a Reynolds number of Re = 5,000. Flow fields have been obtained by means of time-resolved tomographic particle image velocimetry capturing all relevant spatial and temporal scales. The measured threedimensional flow fields have

  6. Broadband diffuse optical spectroscopy assessment of hemorrhage- and hemoglobin-based blood substitute resuscitation

    OpenAIRE

    Lee, Jangwoen; Kim, Jae G.; Mahon, Sari; Tromberg, Bruce J; Mukai, David; Kreuter, Kelly; Saltzman, Darin; Patino, Renee; Goldberg, Robert; Brenner, Matthew

    2009-01-01

    Hemoglobin-based oxygen carriers (HBOCs) are solutions of cell-free hemoglobin (Hb) that have been developed for replacement or augmentation of blood transfusion. It is important to monitor in vivo tissue hemoglobin content, total tissue hemoglobin [THb], oxy- and deoxy-hemoglobin concentrations ([OHb], [RHb]), and tissue oxygen saturation (StO2=[OHb]/[THb]×100%) to evaluate effectiveness of HBOC transfusion. We designed and constructed a broadband diffuse optical spectroscopy (DOS) prototype...

  7. Broadband terahertz spectroscopy: principles, fundamental research and potential for industrial applications

    International Nuclear Information System (INIS)

    Terahertz radiation (also called T-rays) can be employed for spectroscopy and imaging, from the laboratory to industrial applications. In this paper we give an overview of how broadband optoelectronic THz techniques (i.e. using optical lasers to achieve THz generation and detection) can be implemented, and give examples of their unique use in solid-state physics, and in biological and industrial applications. (paper)

  8. Monitoring angiogenesis using a human compatible calibration for broadband near-infrared spectroscopy

    OpenAIRE

    Yang, Runze; Zhang, Qiong; Wu, Ying; Dunn, Jeff F.

    2013-01-01

    Abstract. Angiogenesis is a hallmark of many conditions, including cancer, stroke, vascular disease, diabetes, and high-altitude exposure. We have previously shown that one can study angiogenesis in animal models by using total hemoglobin (tHb) as a marker of cerebral blood volume (CBV), measured using broadband near-infrared spectroscopy (bNIRS). However, the method was not suitable for patients as global anoxia was used for the calibration. Here we determine if angiogenesis could be detecte...

  9. Broadband excitation for short-time impedance spectroscopy

    International Nuclear Information System (INIS)

    Frequency domain impedance measurements are still the common approach in assessing passive electrical properties of cells and tissues. However, due to the time requirements for sweeping over a frequency range for performing spectroscopy, they are not suited for recovering fast impedance changes of biological objects. The use of broad bandwidth excitation and monitoring the response as a function of time will greatly reduce the measurement time. The widespread usage of a square wave excitation is simple but not always the best choice. Here we consider different waveforms for excitation and discuss not only the advantages but also their limitations. Measurements in a miniaturized chamber where frequency and time domain measurements are compared show the suitability of different waveforms as excitation signals for the measurements of bio-impedance. The chirp excitation has been found to be most promising in terms of frequency range, signal-to-noise ratio and crest factor

  10. Structure determination of trans-cinnamaldehyde by broadband microwave spectroscopy.

    Science.gov (United States)

    Zinn, Sabrina; Betz, Thomas; Medcraft, Chris; Schnell, Melanie

    2015-06-28

    The rotational spectrum of trans-cinnamaldehyde ((E)-3-phenyl-2-propenal, C9H8O) was recorded by chirped-pulse Fourier transform microwave spectroscopy in the frequency range of 2-8.5 GHz. The odourant molecule is the essential component of cinnamon oil and causes the characteristic smell. The rotational signatures of two conformers were observed: s-trans-trans- and s-cis-trans-cinnamaldehyde. The rotational spectra of s-trans-trans-cinnamaldehyde and all of its (13)C-monosubstituted species in natural abundance were assigned and the corresponding carbon backbone structure was determined. The second conformer s-cis-trans-cinnamaldehyde is about 9 kJ mol(-1) higher in energy and could also be identified in the spectrum. PMID:26030313

  11. Development of a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer in resonance with transitions in the 900-1550 nm region.

    Science.gov (United States)

    Takaya, Tomohisa; Iwata, Koichi

    2016-07-21

    Charge transfer and charge delocalisation processes play key roles in the functions of large biomolecular systems and organic/inorganic devices. Many of the short-lived transients involved in these processes can be sensitively detected by monitoring their low-energy electronic transitions in the near-IR region. Ultrafast time-resolved near-IR Raman spectroscopy is a promising tool for investigating the structural dynamics of the short-lived transients as well as their electronic dynamics. In this study, we have developed a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer using the Raman pump pulse at 1190 nm and a broadband probe pulse covering the 900-1550 nm region. Spectral and temporal instrument responses of the spectrometer are estimated to be 5 cm(-1) and 120 fs, respectively. Time-resolved near-IR stimulated Raman spectra of poly(3-dodecylthiophene) (P3DDT) are recorded in toluene solution for investigating its structural changes following the photoexcitation. The spectra strongly indicate conformational changes of P3DDT in excited states associated with the elongation of its effective conjugation length. The results on P3DDT fully demonstrate the effectiveness of the newly developed femtosecond time-resolved near-IR stimulated Raman spectrometer. PMID:27327140

  12. Time-resolved photoemission using attosecond streaking

    CERN Document Server

    Nagele, Stefan; Wais, Michael; Wachter, Georg; Burgdörfer, Joachim

    2014-01-01

    We theoretically study time-resolved photoemission in atoms as probed by attosecond streaking. We review recent advances in the study of the photoelectric effect in the time domain and show that the experimentally accessible time shifts can be decomposed into distinct contributions that stem from the field-free photoionization process itself and from probe-field induced corrections. We perform accurate quantum-mechanical as well as classical simulations of attosecond streaking for effective one-electron systems and determine all relevant contributions to the time delay with attosecond precision. In particular, we investigate the properties and limitations of attosecond streaking for the transition from short-ranged potentials (photodetachment) to long-ranged Coulomb potentials (photoionization). As an example for a more complex system, we study time-resolved photoionization for endohedral fullerenes $A$@$\\text{C}_{60}$ and discuss how streaking time shifts are modified due to the interaction of the $\\text{C}_...

  13. Rapid, broadband spectroscopic temperature measurement of hbox {CO}_2 using VIPA spectroscopy

    Science.gov (United States)

    Klose, Andrew; Ycas, Gabriel; Cruz, Flavio C.; Maser, Daniel L.; Diddams, Scott A.

    2016-04-01

    Time-resolved spectroscopic temperature measurements of a sealed carbon dioxide sample cell were realized with an optical frequency comb combined with a two-dimensional dispersive spectrometer. A supercontinuum laser source based on an erbium fiber mode-locked laser was employed to generate coherent light around 2000 nm (5000hbox { cm}^{-1}). The laser was passed through a 12-cm-long cell containing hbox {CO}_2, and the transmitted light was analyzed in a virtually imaged phased array-based spectrometer. Broadband spectra spanning more than 100hbox { cm}^{-1 } with a spectral resolution of roughly 0.075hbox { cm}^{-1} (2.2 GHz) were acquired with an integration period of 2 ms. The temperature of the hbox {CO}_2 sample was deduced from fitting a modeled spectrum to the line intensities of the experimentally acquired spectrum. Temperature dynamics on the timescale of milliseconds were observed with a temperature resolution of 2.6 K. The spectroscopically deduced temperatures agreed with temperatures of the sample cell measured with a thermistor. Potential applications of this technique include quantitative measurement of carbon dioxide concentration and temperature dynamics in gas-phase chemical reactions (e.g., combustion) and plasma diagnostics.

  14. Rapid, broadband spectroscopic temperature measurement of CO2 using VIPA spectroscopy

    CERN Document Server

    Klose, Andrew; Cruz, Flavio C; Maser, Daniel L; Diddams, Scott A

    2016-01-01

    Time-resolved spectroscopic temperature measurements of a sealed carbon dioxide sample cell were realized with an optical frequency comb combined with a two-dimensional dispersive spectrometer. A supercontinuum laser source based on an erbium fiber mode-locked laser was employed to generate coherent light around 2000 nm (5000 cm-1). The laser was passed through a 12-cm long cell containing CO2, and the transmitted light was analyzed in a virtually imaged phased array- (VIPA-) based spectrometer. Broadband spectra spanning more than 100 cm-1 with a spectral resolution of roughly 0.075 cm-1 (2.2 GHz) were acquired with an integration period of 2 ms. The temperature of the CO2 sample was deduced from fitting a modeled spectrum to the line intensities of the experimentally acquired spectrum. Temperature dynamics on the time scale of milliseconds were observed with a temperature resolution of 2.6 K. The spectroscopically-deduced temperatures agreed with temperatures of the sample cell measured with a thermistor. P...

  15. A 3-dimensional time-resolved photothermal deflection ``Mirage'' method

    Science.gov (United States)

    Astrath, N. G. C.; Malacarne, L. C.; Lukasievicz, G. V. B.; Bernabe, H. S.; Rohling, J. H.; Baesso, M. L.; Shen, J.; Bialkowski, S. E.

    2012-02-01

    A three-dimensional time-resolved theory and experiment for photothermal deflection spectroscopy is developed. The heat conduction equations for two semi-infinite media consisting of an opaque sample and a fluid are solved considering temperature and energy flux balance conditions for a Gaussian heat source. The time dependent perpendicular deflection signal is calculated and compared to experimental measurements on glassy carbon and copper samples. Excellent agreement with literature values for thermal diffusivity of the samples is found. The transient behavior is analyzed for different coupling fluids.

  16. Broadband terahertz time-domain spectroscopy : crystalline and glassy drug materials

    International Nuclear Information System (INIS)

    Low-energy IR active modes of glassy and crystalline drug materials were studied by the broadband Terahertz Time Domain Spectroscopy (THz-TDS) in the frequency range from 0.5 to 6.5 THz using a Cherenkov type THz generator. In order to determine the real and imaginary parts of complex dielectric constant, all samples were measured by the transmission using a pure pellet without mixing polyethylene. For glassy indomethacine, the broadband THz spectrum of real part of dielectric constant shows step-wise decrease with the increase of frequency, while the imaginary part shows a broad peak at about 3 THz reflecting quenched glassy disordered structure. The observed spectra of crystalline racemic ketoprofen show the noncoincidence of peak frequencies between low-frequency Raman scattering and THz absorbance spectra. It can be attributed to the fact that the mutual exclusion principle between Raman and IR activities holds below 6 THz

  17. Time-resolved x-ray diagnostics

    International Nuclear Information System (INIS)

    Techniques for time-resolved x-ray diagnostics will be reviewed with emphasis on systems utilizing x-ray diodes or scintillators. System design concerns for high-bandwidth (> 1 GHz) diagnostics will be emphasized. The limitations of a coaxial cable system and a technique for equalizing to improve bandwidth of such a system will be reviewed. Characteristics of new multi-GHz amplifiers will be presented. An example of a complete operational system on the Los Alamos Helios laser will be presented which has a bandwidth near 3 GHz over 38 m of coax. The system includes the cable, an amplifier, an oscilloscope, and a digital camera readout

  18. Stationary and time resolved PL spectroscopy for analysis of ultrafst photoreactions in MALDI and solar cell samples; Stationaere und zeitaufgeloeste Photolumineszenz-Spektroskopie zur Analyse ultraschneller Photoreaktionen in MALDI- und Solarzellenproben

    Energy Technology Data Exchange (ETDEWEB)

    Hoyer, Theo

    2009-02-12

    Stationary and time resolved measurements of photoluminescence (PL) were performed to analyse ultrafast photoreactions in solid MALDI (Matrix-Assisted Laser Desorption/Ionization) and solar cell samples. The investigation of pure cinnamic acid samples resulted in a first-time observation of a PL signature which is controlled by a photodimerisation on a ps- and fs-time scale. Other matrix compounds showed clear evidence of ultrafast photoinduced crystal reactions as well. In analyte/matrix mixtures consisting of angiotensin II and alpha-cyano-4-hydroxycinnamic acid or sinapinic acid, an additional effective PL quenching of matrix monomers was identified. This clearly indicates the existence of a further ultrafast photoreaction which strongly competes with the photodimerisation. The additional reaction is assumed to be a photoisomerisation of matrix monomers and to occur in the immediate vicinity of the analyte molecules. PL measurements on solar cell samples were performed with a P3HT/PCBM-mixture. The results show that within 150 fs about 50% of the P3HT-excitations relax via spontaneous charge transfer to PCBM molecules in this mixture.

  19. Time Resolved Deposition Measurements in NSTX

    Energy Technology Data Exchange (ETDEWEB)

    C.H. Skinner; H. Kugel; A.L. Roquemore; J. Hogan; W.R. Wampler; the NSTX team

    2004-08-03

    Time-resolved measurements of deposition in current tokamaks are crucial to gain a predictive understanding of deposition with a view to mitigating tritium retention and deposition on diagnostic mirrors expected in next-step devices. Two quartz crystal microbalances have been installed on NSTX at a location 0.77m outside the last closed flux surface. This configuration mimics a typical diagnostic window or mirror. The deposits were analyzed ex-situ and found to be dominantly carbon, oxygen, and deuterium. A rear facing quartz crystal recorded deposition of lower sticking probability molecules at 10% of the rate of the front facing one. Time resolved measurements over a 4-week period with 497 discharges, recorded 29.2 {micro}g/cm{sup 2} of deposition, however surprisingly, 15.9 {micro}g/cm{sup 2} of material loss occurred at 7 discharges. The net deposited mass of 13.3 {micro}g/cm{sup 2} matched the mass of 13.5 {micro}g/cm{sup 2} measured independently by ion beam analysis. Monte Carlo modeling suggests that transient processes are likely to dominate the deposition.

  20. Time Resolved Deposition Measurements in NSTX

    International Nuclear Information System (INIS)

    Time-resolved measurements of deposition in current tokamaks are crucial to gain a predictive understanding of deposition with a view to mitigating tritium retention and deposition on diagnostic mirrors expected in next-step devices. Two quartz crystal microbalances have been installed on NSTX at a location 0.77m outside the last closed flux surface. This configuration mimics a typical diagnostic window or mirror. The deposits were analyzed ex-situ and found to be dominantly carbon, oxygen, and deuterium. A rear facing quartz crystal recorded deposition of lower sticking probability molecules at 10% of the rate of the front facing one. Time resolved measurements over a 4-week period with 497 discharges, recorded 29.2 (micro)g/cm2 of deposition, however surprisingly, 15.9 (micro)g/cm2 of material loss occurred at 7 discharges. The net deposited mass of 13.3 (micro)g/cm2 matched the mass of 13.5 (micro)g/cm2 measured independently by ion beam analysis. Monte Carlo modeling suggests that transient processes are likely to dominate the deposition

  1. Broadband x-ray imaging and spectroscopy of the crab nebula and pulsar with NuSTAR

    DEFF Research Database (Denmark)

    Madsen, Kristin K.; Reynolds, Stephen; Harrison, Fiona;

    2015-01-01

    We present broadband (3-78 keV) NuSTAR X-ray imaging and spectroscopy of the Crab nebula and pulsar. We show that while the phase-averaged and spatially integrated nebula + pulsar spectrum is a power law in this energy band, spatially resolved spectroscopy of the nebula finds a break at ~9 keV in...

  2. Broadband cavity enhanced spectroscopy in the ultraviolet spectral region for measurements of nitrogen dioxide and formaldehyde

    Science.gov (United States)

    Washenfelder, R. A.; Attwood, A. R.; Flores, J. M.; Rudich, Y.; Brown, S. S.

    2015-09-01

    Formaldehyde (CH2O) is the most abundant aldehyde in the atmosphere, and strongly affects photochemistry through its photolysis. We describe simultaneous measurements of CH2O and nitrogen dioxide (NO2) using broadband cavity enhanced spectroscopy in the ultraviolet spectral region. The light source consists of a continuous-wave diode laser focused into a Xenon bulb to produce a plasma that emits high-intensity, broadband light. The plasma discharge is optically filtered and coupled into a 1 m optical cavity. The reflectivity of the cavity mirrors is 0.99933 ± 0.00003 (670 ppm loss) at 338 nm, as determined from the known Rayleigh scattering of He and zero air. This mirror reflectivity corresponds to an effective path length of 1.49 km within the 1 m cell. We measure the cavity output over the 315-350 nm spectral region using a grating monochromator and charge-coupled device (CCD) array detector. We use published reference spectra with spectral fitting software to simultaneously retrieve CH2O and NO2 concentrations. Independent measurements of NO2 standard additions by broadband cavity enhanced spectroscopy and cavity ringdown spectroscopy agree within 2 % (slope for linear fit = 0.98 ± 0.03 with r2 = 0.998). Standard additions of CH2O measured by broadband cavity enhanced spectroscopy and calculated based on flow dilution are also well-correlated, with r2 = 0.9998. During constant, mixed additions of NO2 and CH2O, the 30 s measurement precisions (1σ) of the current configuration were 140 and 210 pptv, respectively. The current 1-min detection limit for extinction measurements at 315-350 nm provides sufficient sensitivity for measurement of trace gases in laboratory experiments and ground-based field experiments. Additionally, the instrument provides highly accurate, spectroscopically-based trace gas detection that may complement higher precision techniques based on non-absolute detection methods. In addition to trace gases, this approach will be appropriate for

  3. Resonantly excited high-density exciton gas studiedvia broadbandTHz spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huber, Rupert; Kaindl, Robert A.; Schmid, Ben A.; Chemla, Daniel S.

    2005-06-25

    We report the density-dependent crossover of a resonantly photoexcited exciton gas from insulating to conducting phases. Broadband terahertz spectroscopy gives direct access to the exciton binding energy via intra-excitonic 1s-2p transitions. A strong shift, broadening, and ultimately the disappearance of this resonance occurs with decreasing inter-particle distance. Densities of excitons and unbound electron-hole pairs are followed quantitatively using a model of the composite free-carrier and exciton terahertz conductivity. Comparison with near-infrared absorption changes illustrates a significantly enhanced energy shift and broadening of the intra-excitonic resonance.

  4. Space and time resolved spectroscopy of laser-produced plasmas: A study of density-sensitive x-ray transitions in helium-like and neon-like ions

    International Nuclear Information System (INIS)

    The determination of level populations and detailed population mechanisms in dense plasmas has become an increasingly important problem in atomic physics. In this work, the density variation of line intensities and level populations in aluminum K-shell and molybdenum and silver L-shell emission spectra have been measured from high-powered, laser-produced plasmas. For each case, the density dependence of the observed line emission is due to the effect of high frequency electron-ion collisions on metastable levels. The density dependent line intensities vary greatly in laser-produced plasmas and can be used to extract detailed information concerning the population kinetics and level populations of the ions. The laser-plasmas had to be fully characterized in order to clearly compare the observed density dependence with atomic theory predictions. This has been achieved through the combined use of new diagnostic instruments and microdot targets which provided simultaneously space, time, and spectrally resolved data. The plasma temperatures were determined from the slope of the hydrogen-like recombination continuum. The time resolved electron density profiles were measured using multiple frame holographic interferometry. Thus, the density dependence of K-shell spectral lines could be clearly examined, independent of assumptions concerning the dynamics of the plasma. In aluminum, the electron density dependence of various helium-like line intensity ratios were measured. Standard collisional radiative equilibrium models fail to account for the observed density dependence measured for the ''He/sub α//IC'' ratio. Instead, a quasi-steady state atomic model based on a purely recombining plasma is shown to accurately predict the measured density dependence. This same recombining plasma calculation successfully models the density dependence of the high-n ''He/sub γ//He/sub β/'' and ''He/sub δ//He/sub β/'' helium-like resonance line intensity ratios

  5. Space and time resolved spectroscopy of laser-produced plasmas: A study of density-sensitive x-ray transitions in helium-like and neon-like ions

    Energy Technology Data Exchange (ETDEWEB)

    Young, Bruce Kai Fong

    1988-09-01

    The determination of level populations and detailed population mechanisms in dense plasmas has become an increasingly important problem in atomic physics. In this work, the density variation of line intensities and level populations in aluminum K-shell and molybdenum and silver L-shell emission spectra have been measured from high-powered, laser-produced plasmas. For each case, the density dependence of the observed line emission is due to the effect of high frequency electron-ion collisions on metastable levels. The density dependent line intensities vary greatly in laser-produced plasmas and can be used to extract detailed information concerning the population kinetics and level populations of the ions. The laser-plasmas had to be fully characterized in order to clearly compare the observed density dependence with atomic theory predictions. This has been achieved through the combined use of new diagnostic instruments and microdot targets which provided simultaneously space, time, and spectrally resolved data. The plasma temperatures were determined from the slope of the hydrogen-like recombination continuum. The time resolved electron density profiles were measured using multiple frame holographic interferometry. Thus, the density dependence of K-shell spectral lines could be clearly examined, independent of assumptions concerning the dynamics of the plasma. In aluminum, the electron density dependence of various helium-like line intensity ratios were measured. Standard collisional radiative equilibrium models fail to account for the observed density dependence measured for the ''He/sub ..cap alpha..//IC'' ratio. Instead, a quasi-steady state atomic model based on a purely recombining plasma is shown to accurately predict the measured density dependence. This same recombining plasma calculation successfully models the density dependence of the high-n ''He/sub ..gamma..//He/sub ..beta../'' and ''He/sub delta

  6. Engineered tryptophan in the adenine-binding pocket of catalytic subunit A of A-ATP synthase demonstrates the importance of aromatic residues in adenine binding, forming a tool for steady-state and time-resolved fluorescence spectroscopy

    International Nuclear Information System (INIS)

    The crystallographic structures of the subunit B mutants F427W and F508W of the Pyrococcus horikoshii OT3 of the A1AO ATP synthase reveal that the exact volume of the adenine ribose binding pocket is essential for ATP-/ADP-binding. A reporter tryptophan residue was individually introduced by site-directed mutagenesis into the adenine-binding pocket of the catalytic subunit A (F427W and F508W mutants) of the motor protein A1AO ATP synthase from Pyrococcus horikoshii OT3. The crystal structures of the F427W and F508W mutant proteins were determined to 2.5 and 2.6 Å resolution, respectively. The tryptophan substitution caused the fluorescence signal to increase by 28% (F427W) and 33% (F508W), with a shift from 333 nm in the wild-type protein to 339 nm in the mutant proteins. Tryptophan emission spectra showed binding of Mg-ATP to the F427W mutant with a Kd of 8.5 µM. In contrast, no significant binding of nucleotide could be observed for the F508W mutant. A closer inspection of the crystal structure of the F427W mutant showed that the adenine-binding pocket had widened by 0.7 Å (to 8.70 Å) in comparison to the wild-type subunit A (8.07 Å) owing to tryptophan substitution, as a result of which it was able to bind ATP. In contrast, the adenine-binding pocket had narrowed in the F508W mutant. The two mutants presented demonstrate that the exact volume of the adenine ribose binding pocket is essential for nucleotide binding and even minor narrowing makes it unfit for nucleotide binding. In addition, structural and fluorescence data confirmed the viability of the fluorescently active mutant F427W, which had ideal tryptophan spectra for future structure-based time-resolved dynamic measurements of the catalytic subunit A of the ATP-synthesizing enzyme A-ATP synthase

  7. Effects of sulfation level on the desulfation behavior of pre-sulfated Pt BaO/Al2O3 lean NOx trap catalysts: a combined H2 Temperature-Programmed Reaction, in-situ sulfur K-edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

    International Nuclear Information System (INIS)

    Desulfation by hydrogen of pre-sulfated Pt(2wt%) BaO(20wt%)/Al2O3 with various sulfur loading (S/Ba = 0.12, 0.31 and 0.62) were investigated by combining H2 temperature programmed reaction (TPRX), x-ray photoelectron spectroscopy (XPS), in-situ sulfur K-edge x-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved x-ray diffraction (TR-XRD) techniques. We find that the amount of H2S desorbed during the desulfation in the H2 TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in-situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates were transformed to a BaS phase and remained in the catalyst, rather than being removed as H2S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H2S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H2O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H2S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt BaO/Al2O3 lean NOx trap catalysts is markedly dependent on the sulfation levels.

  8. Incoherent broadband cavity enhanced absorption spectroscopy using supercontinuum and superluminescent diode sources.

    Science.gov (United States)

    Aalto, Antti; Genty, Goëry; Laurila, Toni; Toivonen, Juha

    2015-09-21

    We investigate incoherent broadband cavity enhanced absorption spectroscopy using a tailored supercontinuum source. By tailoring the supercontinuum spectrum to match the high reflectivity bandwidth of the mirrors, we achieve an unprecedented spectral brightness of more than 7 dBm/nm at wavelengths where the effective absorption path length in the cavity exceeds 40 km. We demonstrate the potential of the source in spectrally broadband measurement of weak overtone transitions of carbon dioxide and methane in the near-infrared 1590 nm - 1700 nm range and evaluate its performance against that of a typical superluminescent diode source. Minimum detectable absorption coefficients (3σ) of 2.2 × 10(-9) cm(-1) and 6.2 × 10(-9) cm(-1) are obtained with the supercontinuum and the superluminescent diode sources, respectively. We further develop a spectral fitting method based on differential optical absorption spectroscopy to fully and properly account for the combined effect of absorption line saturation and limited spectral resolution of the detection. The method allows to cope with high dynamic range of absorption features typical of real-world multi-component measurements. PMID:26406720

  9. Broadband on-chip near-infrared spectroscopy based on a plasmonic grating filter array.

    Science.gov (United States)

    Li, Erwen; Chong, Xinyuan; Ren, Fanghui; Wang, Alan X

    2016-05-01

    We demonstrate an ultra-compact, broadband on-chip near-infrared (NIR) spectroscopy system based on a narrow-band plasmonic filter array. The entire filter array, consisting of 28 individual subwavelength metallic gratings, was monolithically integrated in a thin gold film on a quartz substrate, covering a 270 nm spectra from 1510 nm to 1780 nm. In order to achieve a high spectral resolution, extremely narrow slits are created for the gratings with a polymer waveguide layer on top, generating narrow-band guided-mode resonances through coupling with the surface-plasmon resonances of the metallic gratings. Experimental results show that the transmission bands of the filter array have full width at half-maximum of only 7 nm-13 nm, which is sufficient for NIR spectroscopy. The NIR absorption spectroscopy of xylene using the on-chip plasmonic filter array matches very well with the results from conventional Fourier transform infrared spectroscopy, which proves the great potential for NIR sensing applications. PMID:27128037

  10. Enzyme reactions and their time resolved measurements

    International Nuclear Information System (INIS)

    This paper discusses experimental strategies in data collection with the Laue method and summarises recent results using synchrotron radiation. Then, an assessment is made of the progress towards time resolved studies with protein crystals and the problems that remain. The paper consists of three parts which respectively describe some aspects of Laue diffraction, recent examples of structural results from Laue diffraction, and kinetic Laue crystallography. In the first part, characteristics of Laue diffraction is discussed first, focusing on the harmonics problems, spatials problem, wavelength normalization, low resolution hole, data completeness, and uneven coverage of reciprocal space. Then, capture of the symmetry unique reflection set is discussed focusing on the effect of wavelength range on the number of reciprocal lattice points occupying diffracting positions, effect of crystal to film distance and the film area and shape on the number of reflections captured, and effect of crystal symmetry on the number of unique reflections within the number of reflections captured. The second part addresses the determination of the structure of turkey egg white lysozyme, and calcium binding in tomato bushy stunt virus. The third part describes the initiation of reactions in enzyme crystals, picosecond Laue diffraction at high energy storage rings, and detectors. (N.K.)

  11. Time resolved super continuum Cavity Ring-Down Spectroscopy for multicomponent gas detection; Espectroscopia de cavidade ressonante tipo Ring-Down Supercontinuum resolvida no tempo para detecao de multicomponentes gasosos

    Energy Technology Data Exchange (ETDEWEB)

    Nakaema, Walter Morinobu

    2010-07-01

    In this work, we present a variation of the technique CRDS (Cavity Ring-Down Spectroscopy) to obtain simultaneously a multicomponent absorption spectrum in a broad visible range. This new approach uses the Supercontinuum (SC) spectrum (resulting from irradiation of nonlinear media by femtosecond lasers, or simply generated by compact sources) as a light source to illuminate the cavity. In this context it is described the features of the modules assembling a MC-SC-CRDS (Multicomponent Supercontinuum Cavity Ring-Down Spectroscopy): a set of high reflectivity mirrors, the resonant cavity and the detection system. Some problems related to the multimode excitation, stray light, effective use of the dynamic range of the detector, the poor resolution of the instrument to resolve narrow absorption lines are issued. We present the absorption spectra of H{sub 2}O (polyads 4{upsilon}, 4{upsilon} + {delta}) and O{sub 2} (spin-forbidden b-X branch) measured simultaneously by this technique in the visible range and a comparison with the absorption lines based on HITRAN database is made to demonstrate the functionality of this method. (author)

  12. Advances in Low-Frequency 3-color Broadband Coherent Raman Spectroscopy of Condensed Phase Samples

    Science.gov (United States)

    Ujj, Laszlo

    2016-05-01

    Low-frequency dispersive spontaneous Raman spectroscopy is a very useful method to measure phonon frequencies in crystals or characterize collective vibrational motions of macromolecules. The coherent version of the method has not been fully explored yet. It is shown here that the 3-color Broadband Coherent Raman scattering can be a very powerful extension to not only gas phase but condensed phase low frequency (5-500 cm-1) vibrational measurements with large frequency separation between the narrowband and broadband radiation generating the signal. The spectral measurements presented here used volumetric Brag filters for the first time to record coherent Raman spectra. Specific spectral analysis using model independent methods to derive the vibrational information is also presented. The technic can be extended to measure electronic resonance enhanced spectra by tuning only the frequency of the narrowband laser close to the electronic transition frequencies. This makes the method suitable for coherent Raman microscopy. The polarization properties of the signal is also explained and experimentally verified. Financial support from the College of Sciences and Engineering of UWF is acknowledged.

  13. Excited-State Vibrational Coherence in Perylene Bisimide Probed by Femtosecond Broadband Pump-Probe Spectroscopy.

    Science.gov (United States)

    Son, Minjung; Park, Kyu Hyung; Yoon, Min-Chul; Kim, Pyosang; Kim, Dongho

    2015-06-18

    Broadband laser pulses with ultrashort duration are capable of triggering impulsive excitation of the superposition of vibrational eigenstates, giving rise to quantum beating signals originating from coherent wave packet motions along the potential energy surface. In this work, coherent vibrational wave packet dynamics of an N,N'-bis(2,6-dimethylphenyl)perylene bisimide (DMP-PBI) were investigated by femtosecond broadband pump-probe spectroscopy which features fast and balanced data acquisition with a wide spectral coverage of >200 nm. Clear modulations were observed in the envelope of the stimulated emission decay profiles of DMP-PBI with the oscillation frequencies of 140 and 275 cm(-1). Fast Fourier transform analysis of each oscillatory mode revealed characteristic phase jumps near the maxima of the steady-state fluorescence, indicating that the observed vibrational coherence originates from an excited-state wave packet motion. Quantum calculations of the normal modes at the low-frequency region suggest that low-frequency C-C (C═C) stretching motions accompanied by deformation of the dimethylphenyl substituents are responsible for the manifestation of such coherent wave packet dynamics. PMID:25992707

  14. Design of tri-level excitation signals for broadband bioimpedance spectroscopy.

    Science.gov (United States)

    Yang, Yuxiang; Wang, Lianhuan; Wang, Peipei; Yang, Xiufang; Zhang, Fu; Wen, He; Teng, Zhaosheng

    2015-09-01

    Bioimpedance spectroscopy (BIS) measurement methods have been evolving from the traditional frequency-sweep approach to the multi-frequency simultaneous measurement technique which can drastically reduce measuring time and will be increasingly attractive for time-varying biological applications. Multi-frequency mixed (MFM) signals with sparsely distributed spectra are desirable for broadband BIS measurement. This paper proposes a synthesis method to design a series of tri-level MFM signals which contain only three values (+1, 0, -1), and has majority energy distributed on its (2(n))th primary harmonics. Tri-level MFM signals have both high energy efficiency and a low crest factor. An impedance measurement experiment excited by an 8th-order tri-level MFM signal on a RC three-element equivalent model has been performed, and the results on 8 primary harmonic frequencies ranging from 8 to 1024 kHz show a high accuracy with the mean amplitude relative error of 0.41% and mean phase absolute error of 0.18°, which has validated the feasibility of the tri-level MFM signals for broadband BIS measurement. PMID:26261063

  15. Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS – applicability and corrections

    Directory of Open Access Journals (Sweden)

    D. Pöhler

    2009-11-01

    Full Text Available Atmospheric trace gas measurements by cavity assisted long-path absorption spectroscopy are an emerging technology. An interesting approach is the combination of CEAS with broadband light sources, the broadband CEAS (BB-CEAS. BB-CEAS lends itself to the application of the DOAS technique to analyse the derived absorption spectra. While the DOAS approach has enormous advantages in terms of sensitivity and specificity of the measurement, an important implication is the reduction of the light path by the trace gas absorption, since cavity losses due to absorption by gases reduce the quality (Q of the cavity. In fact, at wavelength, where the quality of the BB-CEAS cavity is dominated by the trace gas absorption (especially at very high mirror reflectivity, the average light path will vary nearly inversely with the trace gas concentration and the strength of the band will become only weakly dependent on the trace gas concentration c in the cavity, (the differential optical density being proportional to the logarithm of the trace gas concentration. Only in the limiting case where the mirror reflectivity determines Q at all wavelength, the strength of the band as seen by the CE-DOAS instrument becomes directly proportional to the concentration c. We investigate these relationships in detail and present methods to correct for the cases between the two above extremes, which are of course the important ones in practice.

  16. Earle K. Plyler Prize for Molecular Spectroscopy & Dynamics Lecture: Broadband Rotational Spectroscopy for Chemical Kinetics, Molecular Structure, and Analytical Chemistry

    Science.gov (United States)

    Pate, Brooks

    2013-03-01

    Advances in high-speed digital electronics have enabled a new generation of molecular rotational spectroscopy techniques that provide instantaneous broadband spectral coverage. These techniques use a chirped excitation pulse to coherently excite the molecular sample over a spectral bandwidth of 10 GHz or larger through rapid passage. The subsequent time-domain emission is recorded using high-speed digitizers (up to 100 Gigasample/s) and the frequency domain spectrum is produced by fast Fourier transformation. The chirped-pulse Fourier transform (CP-FT) method has been implemented in the microwave frequency range (2-40 GHz) for studies of cold samples in pulsed jet sources and in the mm-wave/terahertz (THz) frequency range for studies of samples at room-temperature. The method has opened new applications for molecular rotational spectroscopy in the area of chemical kinetics where dynamic rotational spectroscopy is used to measure the rates of unimolecular isomerization reactions in highly excited molecules prepared by pulsed infrared laser excitation. In these applications, the isomerization rate is obtained from an analysis of the overall line shapes which are modified by chemical exchange leading to coalescence behavior similar to the effect in NMR spectroscopy. The sensitivity of the method and the ability to extend it to low frequency (2-8 GHz) have significantly increased the size range of molecules and molecular clusters for structure determination using isotopic substitution to build up the 3D molecular structures atom-by-atom. Application to the structure of water clusters with up to 15 water molecules will be presented. When coupled with advances in solid-state mm-wave/THz devices, this method provides a direct digital technique for analytical chemistry of room-temperature gases based on molecular rotational spectroscopy. These high-throughput methods can analyze complex sample mixtures with unmatched chemical selectivity and short analysis times. Work

  17. Monitoring Network and Interfacial Healing Processes by Broadband Dielectric Spectroscopy: A Case Study on Natural Rubber.

    Science.gov (United States)

    Hernández, M; Grande, A M; van der Zwaag, S; García, S J

    2016-04-27

    Broadband dielectric spectroscopy (BDS) is introduced as a new and powerful technique to monitor network and macroscale damage healing in an elastomer. For the proof of concept, a partially cured sulfur-cured natural rubber (NR) containing reversible disulfides as the healing moiety was employed. The forms of damage healed and monitored were an invisible damage in the rubber network due to multiple straining and an imposed macroscopic crack. The relaxation times of pristine, damaged, and healed samples were determined and fitted to the Havriliak-Negami equation to obtain the characteristic polymer parameters. It is shown that seemingly full mechanical healing occurred regardless the type of damage, while BDS demonstrates that the polymer architecture in the healed material differs from that in the original one. These results represent a step forward in the understanding of damage and healing processes in intrinsic self-healing polymer systems with prospective applications such as coatings, tires, seals, and gaskets. PMID:27057588

  18. Broadband 2D Electronic Spectroscopy Reveals Coupling Between Dark 1Bu- State of Carotenoid and Qx State of Bacteriochlorophyll

    Directory of Open Access Journals (Sweden)

    Scholes Gregory D.

    2013-03-01

    Full Text Available The study of LH2 protein of purple bacteria by broadband 2D electronic spectroscopy is presented. The dark 1Bu- carotenoid state is directly observed in 2D spectra and its role in carotenoid-bacteriochlorophyll interaction is discussed.

  19. Broadband photon time of flight spectroscopy: advanced spectroscopic analysis for ensuring safety and performance of pharmaceutical tablets

    DEFF Research Database (Denmark)

    Kamran, Faisal; Nielsen, Otto Højager Attermann; Andersson-Engels, Stefan;

    2013-01-01

    We report on extended spectroscopic analysis of pharmaceutical tablets performed with broadband photon time-of-flight absorption/scaring spectroscopy. Precise monitoring of absorption and scattering spectra enables cost-efficient monitoring of key safety and performance parameters of the drugs....

  20. Study of broadband THz time-domain spectroscopy at different relative humidity levels

    Institute of Scientific and Technical Information of China (English)

    Chiajen Lin; Ichen Ho; X. C. Zhang

    2012-01-01

    Two detection techniques of broadband terahertz (THz) time-domain spectroscopy-THz air-biased coherent detection (THz-ABCD; from 0.3 to 14 THz) and electro-optical (EO) detection (from 0.3 to 7 THz) - are both performed at several different relative humidity levels.The THz power exponentially decays with the increase in relative humidity.The dynamic range of the main pulse in the time domain linearly decreases as the relative humidity increases from 0% to 40%,and linear fittings show that the slopes are -0.017 and -0.019 for THz-ABCD and EO detection,respectively.Because of the multiple reflections caused by the crystal in the common EO detection,THz-ABCD has better spectral resolution (17 GHz) than that of EO detection (170 GHz).The spectrum of water vapor absorption measured by THz-ABCD is also compared with that measured by the Fourier transform infrared spectroscopy (FTIR).

  1. Time resolved excitation dynamics in emeraldine base

    Czech Academy of Sciences Publication Activity Database

    Menšík, Miroslav; Rais, David; Pfleger, Jiří

    2015-01-01

    Roč. 456, 29 July (2015), s. 79-84. ISSN 0301-0104. [International Conference Electronic and Related Properties of Organic Solids /13./ - ERPOS 2014. Świeradów Zdrój, 06.07.2014-10.07.2014] R&D Projects: GA MŠk LH12186; GA MŠk(CZ) LD14011; GA ČR GAP108/12/1143 Grant ostatní: European Commission(XE) COST Action MP1202 HINT Institutional support: RVO:61389013 Keywords : polyaniline * emeraldine base * transient absorption spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.652, year: 2014

  2. Attosecond Time-Resolved Autoionization of Argon

    International Nuclear Information System (INIS)

    Autoionization of argon atoms was studied experimentally by transient absorption spectroscopy with isolated attosecond pulses. The peak position, intensity, linewidth, and shape of the 3s3p6np 1P Fano resonance series (26.6-29.2 eV) were modified by intense few-cycle near infrared laser pulses, while the delay between the attosecond pulse and the laser pulse was changed by a few femtoseconds. Numerical simulations revealed that the experimentally observed splitting of the 3s3p64p 1P line is caused by the coupling between two short-lived highly excited states in the strong laser field.

  3. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

    DEFF Research Database (Denmark)

    Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.;

    2011-01-01

    such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16...

  4. Time-resolved transient optical absorption study of constitutional-dynamic conjugated polymers

    Czech Academy of Sciences Publication Activity Database

    Pfleger, Jiří; Rais, David; Vitvarová, T.; Vohlídal, J.; Svoboda, J.

    Pisa : European Polymer Federation, 2013. O7-3. [European Polymer Congress - EPF 2013. 16.06.2013-21.06.2013, Pisa] R&D Projects: GA ČR GAP108/12/1143; GA TA ČR TE01020022 Institutional support: RVO:61389013 Keywords : time-resolved optical spectroscopy * conjugated polymers Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering

  5. A time-resolved fluorescence study of matrix-isolated Ag 2

    Science.gov (United States)

    Hebert, T.; Kolb, D. M.; Rotermund, H. H.; Schriever, U.; Wiggenhauser, H.

    1990-02-01

    The nanosecond lifetimes of the A, B and C states of Ag 2 in Ar, Kr and Xe matrices were determined by time-resolved emission spectroscopy. From an analysis of the rise and decay times after pulsed optical excitation, the non-radiative relaxation channel between the B and A states was quantitatively established.

  6. Time-resolved Fourier transform infrared spectra of Sr: h-, g-levels and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Ferus, Martin; Chernov, Vladislav E.; Zanozina, Ekaterina M.; Juha, Libor

    2013-01-01

    Roč. 129, NOV 2013 (2013), s. 324-332. ISSN 0022-4073 R&D Projects: GA ČR GAP208/10/2302 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Time-resolved FTIR spectroscopy * Strontium * Rydberg states Subject RIV: CF - Physical ; Theoretical Chemistry; BH - Optics, Masers, Laser s (FZU-D) Impact factor: 2.288, year: 2013

  7. Time-Resolved Remote Raman Spectroscopy for Venus Exploration

    Science.gov (United States)

    Sharma, S. K.; Misra, A. K.; Acosta-Maeda, T. E.; Dyer, M. D.; Clegg, S. M.; Wiens, R. C.

    2015-04-01

    We describe a compact gatable planetary Raman spectrograph developed at the University of Hawaii that is suitable for detecting low concentrations of relevant minerals in a basaltic glass matrix on the Venus surface from a lander.

  8. Pulsed Green Laser for Time Resolved Raman Spectroscopy Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I effort will demonstrate the feasibility of developing a fully packaged, efficient, short pulse, high repetition rate frequency doubled micro-chip...

  9. Resonant and time-resolved spin noise spectroscopy

    Science.gov (United States)

    Pursley, Brennan C.; Song, X.; Sih, V.

    2015-11-01

    We demonstrate a method to extend the range of pulsed laser spin noise measurements to long spin lifetimes. We use an analog detection scheme with a bandwidth limited only by laser pulse duration. Our model uses statistics and Bloch-Torrey equations to extract the Lande g-factor, Faraday cross-section σ F , and spin lifetime τ s , while accounting for finite detector response. Varying the magnetic field with a fixed probe-probe delay yields τ s when it is longer than the laser repetition period. Varying the probe-probe delay with a fixed field produces a time-domain measurement of the correlation function.

  10. Time Resolved X Ray Scattering and Spectroscopy In Materials Science

    International Nuclear Information System (INIS)

    The study of materials relevant for energy applications covers a large array of experimental techniques, time domains and types of materials. In this paper, we will discuss some of the issues that we have encountered and describe some experiments and which combinations of techniques were used. The paper mainly presents results based on synchrotron radiation X ray techniques but also shows how important it is to complement their results with those obtained through non X ray techniques in order to obtain a comprehensive picture of the time evolution of the materials under study. (author)

  11. Time-resolved spectroscopy in the Rijnhuizen Tokamak Project tokamak

    Energy Technology Data Exchange (ETDEWEB)

    Box, F.M.A.; Kolk, E. van de [Associatie Euratom-FOM, Nieuwegein (Netherlands). FOM-Instituut voor Plasmafysica; Howard, J. [Plasma Research Laboratory, Research School of Physical Science and Engineering, Australian National University, Canberra 0200 (Australia); Meijer, F.G. [Physics Faculty, University of Amsterdam, Amsterdam (Netherlands)

    1997-03-01

    At the Rijnhuizen Tokamak Project tokamak spectrometers are used to diagnose the velocity distribution and abundances of impurity ions. Quantities can be measured as a function of time, and the temporal resolution depends on the line emissivity and can be as good as 0.2 ms for the strongest lines. Several spectrometers, equipped with a charge-coupled device array, are being used with spectral ranges in the visible, the vacuum UV and the extreme UV. (orig.)

  12. Time-resolved pulsed EPR: microwave and optical detection

    Energy Technology Data Exchange (ETDEWEB)

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Time-resolved pulsed EPR spectrometers are described. EPR spectra, kinetic profiles, and relaxation studies are used to illustrate some capabilities of the pulsed EPR experiment. Optical detection of time-resolved EPR spectra of radical ion pairs is used to study radical-ion recombination kinetics, recombination pathways, and the structure of radical anions and cations. 17 figures.

  13. Time-resolved pulsed EPR: microwave and optical detection

    International Nuclear Information System (INIS)

    Time-resolved pulsed EPR spectrometers are described. EPR spectra, kinetic profiles, and relaxation studies are used to illustrate some capabilities of the pulsed EPR experiment. Optical detection of time-resolved EPR spectra of radical ion pairs is used to study radical-ion recombination kinetics, recombination pathways, and the structure of radical anions and cations. 17 figures

  14. Time resolved excitation dynamics in emeraldine base

    Energy Technology Data Exchange (ETDEWEB)

    Menšík, Miroslav, E-mail: mensik@imc.cas.cz; Rais, David; Pfleger, Jiří

    2015-07-29

    Highlights: • fs-transient absorption spectra of emeraldine base of polyaniline pumped at 700 nm. • Kinetic master equations for experimental data. • Formation of charge transfer states within 50 fs. Non-radiative decay (0.5 ps). • Phenyl rings relaxation (2.1 ps). • Formation of long-lived polarons (∼ns). - Abstract: Using femtosecond pump–probe transient absorption spectroscopy (wavelengths 330–800 nm), we observed and explained excited state, charge transfer and polaron state dynamics in emeraldine base form of polyaniline in dimethyl sulfoxide solution. The excited state created by a pump pulse (700 nm) in the quinoid absorption Q-band loses its initial symmetry by subsequent energy transition to a charge transfer state within 50 fs. The hot charge transfer state either recombines non-radiatively into the ground state with decay time constant 0.55 ps or transfers into a relaxed state corresponding to the relaxed phenyl geometry during ca 2.1 ps. This relaxed state shows a prolonged lifetime of about 6.5 ps before its recombination to the ground state. However, a small amount of long-lived polarons with lifetime of about 2 ns in air and with lifetime longer than 6 ns in the solution bubbled with dry N{sub 2} was detected.

  15. Molecular dynamics of amorphous pharmaceutical fenofibrate studied by broadband dielectric spectroscopy$

    Institute of Scientific and Technical Information of China (English)

    U. Sailaja; M. Shahin Thayyil; N.S. Krishna Kumar; G. Govindaraj

    2016-01-01

    Fenofibrate is mainly used to reduce cholesterol level in patients at risk of cardiovascular disease. Thermal transition study with the help of differential scanning calorimetry (DSC) shows that the aforesaid active pharmaceutical ingredient (API) is a good glass former. Based on our DSC study, the molecular dynamics of this API has been carried out by broadband dielectric spectroscopy (BDS) covering wide temperature and frequency ranges. Dielectric measurements of amorphous fenofibrate were per-formed after its vitrification by fast cooling from a few degrees above the melting point (Tm ¼ 354.11 K) to deep glassy state. The sample does not show any crystallization tendency during cooling and reaches the glassy state. The temperature dependence of the structural relaxation has been fitted by single Vogel–Fulcher–Tamman (VFT) equation. From VFT fit, glass transition temperature (Tg) was estimated as 250.56 K and fragility (m) was determined as 94.02. This drug is classified as a fragile glass former. Deviations of experimental data from Kohlrausch–Williams–Watts (KWW) fits on high-frequency flank of α-peak indicate the presence of an excess wing in fenofibrate. Based on Ngai's coupling model, we identified the excess wing as true Johari–Goldstein (JG) process. Below the glass transition temperature one can clearly see a secondary relaxation (γ) with an activation energy of 32.67 kJ/mol.

  16. Broadband spectroscopy of the electromagnetic properties of aqueous ferrofluids for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Bellizzi, G., E-mail: gbellizz@unina.i [Dipartimento di Ingegneria Biomedica, Elettronica e delle Telecomunicazioni, Universita di Napoli Federico II, via Claudio 21, 80125 Napoli (Italy); Bucci, O.M. [Dipartimento di Ingegneria Biomedica, Elettronica e delle Telecomunicazioni, Universita di Napoli Federico II, via Claudio 21, 80125 Napoli (Italy); Istituto per il Rilevamento Elettromagnetico dell' Ambiente - Consiglio Nazionale delle Ricerche, via Diocleziano 328, I-80124 Napoli (Italy); Capozzoli, A. [Dipartimento di Ingegneria Biomedica, Elettronica e delle Telecomunicazioni, Universita di Napoli Federico II, via Claudio 21, 80125 Napoli (Italy)

    2010-10-15

    This paper presents the results of a broadband spectroscopy study, over the frequency range 1 MHz-2 GHz, of the electromagnetic properties of a ferrofluid consisting of magnetite nanoparticles, with a mean magnetic size of 10 nm, dispersed in water. An innovative measurement approach and apparatus, allowing an accurate determination of the permeability, even in presence of a large permittivity, have been developed to characterize the suspension. The results obtained show a significant magnetic response over the whole analyzed frequency range, with a good agreement with the theoretical models describing the magnetization dynamics of these systems. Moreover, a strong dielectric response has been detected, which is in satisfactory agreement with the models developed to describe the dielectric behavior of charged nanoparticles suspended in aqueous solution. This result implies that measurement techniques able to determine both the permittivity and permeability become mandatory for a reliable determination of the magnetic properties of aqueous ferrofluids. The accuracy of the determined permeability spectrum is estimated to be of the order of few percent, so these results provide a reliable experimental basis to estimate how fruitful the use of magnetic nanoparticles can be in relevant biomedical applications.

  17. Broadband spectroscopy of the electromagnetic properties of aqueous ferrofluids for biomedical applications

    Science.gov (United States)

    Bellizzi, G.; Bucci, O. M.; Capozzoli, A.

    2010-10-01

    This paper presents the results of a broadband spectroscopy study, over the frequency range 1 MHz-2 GHz, of the electromagnetic properties of a ferrofluid consisting of magnetite nanoparticles, with a mean magnetic size of 10 nm, dispersed in water. An innovative measurement approach and apparatus, allowing an accurate determination of the permeability, even in presence of a large permittivity, have been developed to characterize the suspension. The results obtained show a significant magnetic response over the whole analyzed frequency range, with a good agreement with the theoretical models describing the magnetization dynamics of these systems. Moreover, a strong dielectric response has been detected, which is in satisfactory agreement with the models developed to describe the dielectric behavior of charged nanoparticles suspended in aqueous solution. This result implies that measurement techniques able to determine both the permittivity and permeability become mandatory for a reliable determination of the magnetic properties of aqueous ferrofluids. The accuracy of the determined permeability spectrum is estimated to be of the order of few percent, so these results provide a reliable experimental basis to estimate how fruitful the use of magnetic nanoparticles can be in relevant biomedical applications.

  18. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

    International Nuclear Information System (INIS)

    We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm−1. We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions

  19. Molecular dynamics of amorphous pharmaceutical fenofibrate studied by broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    U. Sailaja

    2016-06-01

    Full Text Available Fenofibrate is mainly used to reduce cholesterol level in patients at risk of cardiovascular disease. Thermal transition study with the help of differential scanning calorimetry (DSC shows that the aforesaid active pharmaceutical ingredient (API is a good glass former. Based on our DSC study, the molecular dynamics of this API has been carried out by broadband dielectric spectroscopy (BDS covering wide temperature and frequency ranges. Dielectric measurements of amorphous fenofibrate were performed after its vitrification by fast cooling from a few degrees above the melting point (Tm=354.11 K to deep glassy state. The sample does not show any crystallization tendency during cooling and reaches the glassy state. The temperature dependence of the structural relaxation has been fitted by single Vogel–Fulcher–Tamman (VFT equation. From VFT fit, glass transition temperature (Tg was estimated as 250.56 K and fragility (m was determined as 94.02. This drug is classified as a fragile glass former. Deviations of experimental data from Kohlrausch–Williams–Watts (KWW fits on high-frequency flank of α-peak indicate the presence of an excess wing in fenofibrate. Based on Ngai׳s coupling model, we identified the excess wing as true Johari–Goldstein (JG process. Below the glass transition temperature one can clearly see a secondary relaxation (γ with an activation energy of 32.67 kJ/mol.

  20. Blend uniformity analysis of pharmaceutical products by Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS).

    Science.gov (United States)

    Fitzpatrick, Dara; Scanlon, Eoin; Krüse, Jacob; Vos, Bastiaan; Evans-Hurson, Rachel; Fitzpatrick, Eileen; McSweeney, Seán

    2012-11-15

    Blend uniformity analysis (BUA) is a routine and highly regulated aspect of pharmaceutical production. In most instances, it involves quantitative determination of individual components of a blend in order to ascertain the mixture ratio. This approach often entails the use of costly and sophisticated instrumentation and complex statistical methods. In this study, a new and simple qualitative blend confirmatory test is introduced based on a well known acoustic phenomenon. Several over the counter (OTC) product powder blends are analysed and it is shown that each product has a unique and highly reproducible acoustic signature. The acoustic frequency responses generated during the dissolution of the product are measured and recorded in real time. It is shown that intra-batch and inter-batch variation for each product is either insignificant or non-existent when measured in triplicate. This study demonstrates that Broadband Acoustic Resonance Dissolution Spectroscopy or BARDS can be used successfully to determine inter-batch variability, stability and uniformity of powder blends. This is just one application of a wide range of BARDS applications which are more cost effective and time efficient than current methods. PMID:22884840

  1. The σ-hole interaction between sulfur hexafluoride and ammonia characterised by broadband rotational spectroscopy.

    Science.gov (United States)

    Bittner, Dror M; Zaleski, Daniel P; Stephens, Susanna L; Walker, Nicholas R; Legon, Anthony C

    2015-08-24

    A weakly-bound complex of SF6 and NH3 is generated within an expanding gas jet and characterised by broadband rotational spectroscopy. The spectra of isotopologues (32) SF6 ⋅⋅⋅(14) NH3 , (32) SF6 ⋅⋅⋅(14) ND3 , (32) SF6 ⋅⋅⋅(15) NH3 and (34) SF6 ⋅⋅⋅(15) NH3 are observed and assigned to determine the spectroscopic parameters. These parameters are consistent with the complex having a C3v symmetric rotor geometry, in which the nitrogen atom of NH3 coordinates to SF6 such that the C3v axis of the NH3 sub-unit is aligned with a local C3 axis on the SF6 sub-unit. The geometry of the complex is rationalized in terms of a σ-hole interaction. The observed spectra and ab initio calculations also reveal evidence of internal dynamics involving internal rotation of one monomer sub-unit with respect to the other about the symmetry axis of the complex. PMID:26175274

  2. Broadband Bioimpedance Spectroscopy Based on a Multifrequency Mixed Excitation and Nuttall Windowed FFT Algorithm

    Directory of Open Access Journals (Sweden)

    Yuxiang Yang

    2014-01-01

    Full Text Available Bioimpedance spectroscopy (BIS has become an important clinical indicator for monitoring the pathological status of biological tissues, and multifrequency simultaneous measurement of BIS may provide more accurate diagnostic information compared with the traditional frequency-sweep measurement technology. This paper proposes a BIS multifrequency simultaneous measurement method based on multifrequency mixed (MFM signal excitation and a Nuttall windowed interpolation FFT algorithm. Firstly, the excitation source adopts the nine-frequency MFM signal f(9,t, which has excellent spectral characteristic and is very suitable for BIS measurement. On this basis, a Nuttall window is adopted to truncate sample data, and an interpolation FFT algorithm based on Nuttall window is built to perform spectral analysis, in which the parameter correction formula is provided based on polynomial approximation. A BIS measurement simulation experiment is performed on an RC three-element equivalent circuit, and results on the 9 primary harmonic frequencies ranging from 3.9 kHz to 1 MHz show a high accuracy with the impedance amplitude relative error |Ez|<0.3%, and the phase absolute error |Ep|<0.1°. This paper validates the feasibility of BIS multifrequency simultaneous measurement method and establishes an algorithm foundation for the development of practical broadband BIS measurement system.

  3. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Aritra [Department of Chemistry, James Franck Institute, and Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Tokmakoff, Andrei, E-mail: tokmakoff@uchicago.edu [Department of Chemistry, James Franck Institute, and Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States)

    2015-11-21

    We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm{sup −1}. We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions.

  4. Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS – applicability and corrections

    Directory of Open Access Journals (Sweden)

    D. Pöhler

    2008-12-01

    Full Text Available Atmospheric trace gas measurements by cavity assisted long-path absorption spectroscopy are an emerging technology. An interesting approach is the combination of CEAS with broad band light sources, the broad-band CEAS (BB-CEAS. BB-CEAS lends itself to the application of the DOAS technique to analyse the derived absorption spectra. While the DOAS approach has enormous advantages in terms of sensitivity and specificity of the measurement, an important implication is the reduction of the light path by the trace gas absorption, since cavity losses due to absorption by gases reduce the quality (Q of the cavity. In fact, at wavelength, where the quality of the BB-CEAS cavity is dominated by the trace gas absorption (esp. at very high mirror reflectivity, the light path will vary inversely with the trace gas concentration and the strength of the band will become nearly independent of the trace gas concentration c in the cavity, rendering the CEAS Method useless for trace gas measurements. Only in the limiting case where the mirror reflectivity determines Q at all wavelength, the strength of the band as seen by the BB-CEAS instrument becomes proportional to the concentration c. We investigate these relationships in detail and present methods to correct for the cases between the two above extremes, which are of course the important ones in practice.

  5. Monitoring angiogenesis using a human compatible calibration for broadband near-infrared spectroscopy

    Science.gov (United States)

    Yang, Runze; Zhang, Qiong; Wu, Ying; Dunn, Jeff F.

    2013-01-01

    Angiogenesis is a hallmark of many conditions, including cancer, stroke, vascular disease, diabetes, and high-altitude exposure. We have previously shown that one can study angiogenesis in animal models by using total hemoglobin (tHb) as a marker of cerebral blood volume (CBV), measured using broadband near-infrared spectroscopy (bNIRS). However, the method was not suitable for patients as global anoxia was used for the calibration. Here we determine if angiogenesis could be detected using a calibration method that could be applied to patients. CBV, as a marker of angiogenesis, is quantified in a rat cortex before and after hypoxia acclimation. Rats are acclimated at 370-mmHg pressure for three weeks, while rats in the control group are housed under the same conditions, but under normal pressure. CBV increased in each animal in the acclimation group. The mean CBV (%volume/volume) is 3.49%±0.43% (mean±SD) before acclimation for the experimental group, and 4.76%±0.29% after acclimation. The CBV for the control group is 3.28%±0.75%, and 3.09%±0.48% for the two measurements. This demonstrates that angiogenesis can be monitored noninvasively over time using a bNIRS system with a calibration method that is compatible with human use and less stressful for studies using animals.

  6. Time-resolved materials science opportunities using synchrotron x-ray sources

    International Nuclear Information System (INIS)

    The high brightness, high intensity, and pulsed time-structure of synchrotron sources provide new opportunities for time-resolved x-ray diffraction investigations. With third generation synchrotron sources coming on line, high brilliance and high brightness are now available in x-ray beams with the highest flux. In addition to the high average flux, the instantaneous flux available in synchrotron beams is greatly enhanced by the pulsed time structure, which consists of short bursts of x-rays that are separated by ∼tens to hundreds of nanoseconds. Time-resolved one- and two-dimensional position sensitive detection techniques that take advantage of synchrotron radiation for materials science x-ray diffraction investigations are presented, and time resolved materials science applications are discussed in terms of recent diffraction and spectroscopy results and materials research opportunities

  7. Time-resolved scanning tunnelling microscopy for molecular science

    International Nuclear Information System (INIS)

    Time-resolved scanning tunnelling microscopy (STM) and its application in molecular science are reviewed. STM can image individual atoms and molecules and thus is able to observe the results of molecular processes such as diffusion, desorption, configuration switching, bond-breaking and chemistry, on the atomic scale. This review will introduce time-resolved STM, its experimental limitations and implementations with particular emphasis on thermally activated and tunnelling current induced molecular processes. It will briefly examine the push towards ultrafast imaging. In general, results achieved by time-resolved STM demonstrate the necessity of both space and time resolution for fully characterizing molecular processes on the atomic scale.

  8. Time-resolved Chemical Imaging of Molecules by High-order Harmonics and Ultrashort Rescattering Electrons

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Chii Dong [Kansas State Univ., Manhattan, KS (United States)

    2016-03-21

    Directly monitoring atomic motion during a molecular transformation with atomic-scale spatio-temporal resolution is a frontier of ultrafast optical science and physical chemistry. Here we provide the foundation for a new imaging method, fixed-angle broadband laser-induced electron scattering, based on structural retrieval by direct one-dimensional Fourier transform of a photoelectron energy distribution observed along the polarization direction of an intense ultrafast light pulse. The approach exploits the scattering of a broadband wave packet created by strong-field tunnel ionization to self-interrogate the molecular structure with picometre spatial resolution and bond specificity. With its inherent femtosecond resolution, combining our technique with molecular alignment can, in principle, provide the basis for time-resolved tomography for multi-dimensional transient structural determination.

  9. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy; Neuartige Lanthanoid-dotierte mikro- und mesoporoese Feststoffe. Charakterisierung von Ion-Wirt-Wechselwirkungen, Speziesverteilung und Lumineszenzeigenschaften mittels zeitaufgeloester Lumineszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Gessner, Andre

    2010-12-15

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the {sup 5}D{sub 0}-{sup 7}F{sub 0}-transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the

  10. Adsorption of cytochrome c to silica surfaces studied using evanescent wave broadband cavity-enhanced absorption spectroscopy

    Science.gov (United States)

    Moore, L. J.; van der Sneppen, L.; Peverall, R.; Hancock, G.; Ritchie, G. A. D.

    2010-08-01

    The adsorption of cytochrome c (cyt c) to a silica surface has been studied by use of evanescent wave broadband cavityenhanced absorption spectroscopy (EW-BBCEAS). Visible radiation from a supercontinuum source is coupled into an optical cavity consisting of a pair of broadband high reflectivity mirrors, and a total internal reflection (TIR) event at the prism/water interface. Aqueous solutions of cyt c are placed onto the TIR footprint on the prism surface and the subsequent protein adsorption is probed by the resulting evanescent wave. The time integrated cavity output is directed into a spectrometer, where it is dispersed and analysed. The high spectral brilliance of the SC affords a baseline noise comparable to evanescent wave cavity ring-down spectroscopy (EW-CRDS), and the broadband nature of the source allows observation of a wide spectral range (ca 250 nm in the visible). The system is calibrated by measuring the absorption spectra of dyes of a known absorbance. Absorption spectra of cyt c are obtained for both S and P polarized radiation, allowing information about the orientation of the adsorbed protein to be extracted.

  11. Advances in Time-Resolved Tomographic Particle Image Velocimetry

    OpenAIRE

    Lynch, K.P.

    2015-01-01

    This thesis details advanced developments in 3-D particle image velocimetry (PIV) based on the tomographic PIV technique, with an emphasis on time-resolved experiments. Tomographic PIV is a technique introduced in 2006 to measure the flow velocity in a three-dimensional volume. When measurements are performed at a rate high enough to sample the dynamical evolution of the flow, the measurement is considered time-resolved. The present work begins with a description of developments in tomographi...

  12. Time-resolved luminescence studies of Eu3+ in soda-lime silicate glasses

    International Nuclear Information System (INIS)

    Soda-lime glasses doped with Eu3+ were synthesized using a variety of compositions, namely changing the fraction of CaO or Eu2O3. Those glasses were characterized with several techniques, including ellipsometry, UV–vis–NIR absorption spectroscopy, steady-state photoluminescence spectroscopy and time-resolved luminescence. The compositions' effects on optical properties such as refraction indexes, Eu3+ oscillator strengths and luminescence lifetimes were accessed from the analysis of the experimental results. Judd–Ofelt theory was used to analyze all these aspects, which allow the detection of a mismatch of optical properties from absorption and emission spectroscopy. This mismatch was confirmed from the time-resolved data, showing the existence of two different spectroscopic Eu3+ species. From those results it is concluded that there is evidence for lanthanide aggregation, giving rise to self-quenching effects that may be described through resonance energy transfer mechanisms. The difference between luminescence lifetimes for isolated and aggregated Eu(III) is interpreted as due to different interactions with oxygen in the matrix, namely degree of covalency of the Eu–O bond and point group symmetry of the lanthanide. -- Highlights: • Time resolved luminescence studies of Eu(III) in soda-lime silicate glass show the existence of two different species. • Mismatch of Judd–Ofelt parameters are obtained from absorption and emission spectroscopy. • Eu(III) has less clustering tendency when Eu2O3 concentration decreases and when CaO concentration increases

  13. Time-resolved study of Higgs mode in superconductors

    Science.gov (United States)

    Shimano, Ryo

    The behavior of superconductors far from equilibrium has been intensively studied over decades. Goals of these studies are the elucidation of bosonic fluctuations essential for the pairing mechanisms, the manifestation of competing orders or hidden phases, and the optical manipulation of superconductivity. The study of collective modes is crucially important for these perspectives as it provides the information on the dynamics of order parameters in non-equilibirium states. Generally, collective modes in ordered phases associated with spontaneous symmetry breaking are classified into 1) gapless phase modes and 2) gapped amplitude modes. In superconductors, the phase mode is eaten by gauge field, according to the Anderson-Higgs mechanism. The remaining amplitude mode is recently termed as Higgs mode from its analogy to the Higgs boson in particle physics. Despite its long history of investigation, unambiguous observation of Higgs mode has remained elusive. This is because the Higgs mode does not have a charge nor electric dipole and therefore it does not couple directly to the electromagnetic field. Here we report on our recent observation of Higgs mode in s-wave superconductors by using THz-pump and THz-probe spectroscopy technique. After nonadiabatic excitation near the superconducting gap energy with monocycle THz pulses, Higgs mode was observed as oscillations in the transmission of THz probe pulse. The resonant nonlinear coupling between the Higgs mode and coherent radiation field was also discovered, resulting in an efficient third order harmonic generation of the incident THz radiation. The extension of experiments to multiband superconductors and unconventional superconductors will be discussed. Time-resolved study of Higgs mode in superconductors.

  14. SPACE-TIME RESOLVED DIAGNOSTICS OF RADIO FREQUENCY GLOW DISCHARGE KINETICS

    OpenAIRE

    Gottscho, R.

    1987-01-01

    Three applications of space-time resolved spectroscopy to the study of plasma processes are reviewed briefly. Each application emphasizes a different aspect of plasma chemistry : heterogeneous reactions, homogeneous reactions, and charged-particle transport. Spatially-resolved concentration profiles of reactants near surfaces provides estimates for heterogeneous reaction rates. This is demonstrated using data for CF2 molecules near Si and O atoms near Al, graphite, and kapton. Space-time reso...

  15. Femtosecond time-resolved molecular multiphoton ionization: the Na_2 system

    OpenAIRE

    Baumert, Thomas,; Grosser, M.; Thalweiser, Rainer; Gerber, Gustav

    1991-01-01

    We report here the first experimental study of femtosecond time-resolved molecular multiphoton ionization. Femtosecond pump-probe techniques are combined with time-of-flight spectroscopy to measure transient ionization spectra of Na_2 in a molecular-beam experiment. The wave-packet motions in different molecular potentials show that incoherent contributions from direct photoionization of a singly excited state and from excitation and autoionization of a bound doubly excited molecu...

  16. Glucose Sensing by Time-Resolved Fluorescence of Sol-Gel Immobilized Glucose Oxidase

    OpenAIRE

    Maria Lepore; Raffaele Velotta; Carlo Altucci; Sergio De Nicola; Bartolomeo Della Ventura; Rosario Esposito; Damiano Gustavo Mita

    2011-01-01

    A monolithic silica gel matrix with entrapped glucose oxidase (GOD) was constructed as a bioactive element in an optical biosensor for glucose determination. Intrinsic fluorescence of free and immobilised GOD was investigated in the visible range in presence of different glucose concentrations by time-resolved spectroscopy with time-correlated single-photon counting detector. A three-exponential model was used for analysing the fluorescence transients. Fractional intensities and mean lifetime...

  17. Chain Dynamics in Solid Polymers and Polymerizing Systems as Revealed by Broadband Dielectric Spectroscopy

    Science.gov (United States)

    Williams, Graham

    2008-08-01

    A number of techniques are used to study the chain-dynamics of solid polymers, including those of dielectric relaxation [1-4], dynamic mechanical thermal analysis (DMTA) [1, 5], multinuclear NMR relaxations [6], quasi-elastic dynamic light scattering [7] and neutron scattering [8] (QELS & QENS) and transient fluorescence depolarization (TFD) [9]. Each technique has its own particular probe of the dynamics in a material. e.g. dielectric relaxation gives information on the angular motions of molecular chain-dipoles (for dipole relaxation) and the translational motions of ions (for f-dependent electrical conduction); NMR relaxations relate to the angular motions of chemical bonds; QELS relates to fluctuations in local refractive index; QENS to the time-dependent van Hove correlation function (suitably-defined) for proton-containing groups; TFD to the angular motions of fluorescent groups in a chain. Due to its relevance to practical applications of materials, DMTA is pre-eminent among the many physical techniques applied to solid polymers, but interpretations of behaviour in terms of molecular properties remain difficult since the direct link between an applied macroscopic stress and the molecular response of polymer chains in a bulk material remains an unsolved problem. Of the above techniques, Broadband Dielectric Spectroscopy (BDS) offers several advantages. (a) Materials may be studied in the frequency range 10-6 to 1010 Hz, over wide ranges of temperature and applied pressure, using commercially-available instrumentation. (b) Since the electrical capacitance of a film is inversely proportional its thickness, free-standing and supported films may be studied down to nm-thicknesses, giving e.g. information on the behaviour of the dynamic Tg as sample thickness approaches molecular dimensions. (c) Theoretical interpretations of dielectric relaxation and a.c. conduction are well-established in terms of Fourier transforms of molecular time correlation functions (TCFs

  18. Broadband terahertz time-domain spectroscopy of ferroelectric LiTaO{sub 3}: Phonon-polariton dispersion

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, Seiji, E-mail: kojima@bk.tsukuba.ac.jp; Mori, Tatsuya, E-mail: kojima@bk.tsukuba.ac.jp [Division of Materials Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan)

    2014-11-05

    The lowest frequency IR active A{sub 1}(z) and E(x) modes of a ferroelectric congruent lithium tantalate crystal were studied by the broadband polarized Terahertz Time-Domain Spectroscopy using the coherent THz radiation from 0.2 to 6.5 THz. The dispersion relations of the real and imaginary parts of a polariton wave vector were determined from the complex extraordinary and ordinary refractive indices for the A{sub 1}(z) and E(x) symmetry phonon-polaritons, respectively. The observed complex dispersion relations of two symmetries are in agreement within the experimental uncertainty with the calculated dispersion curves by the damped harmonic oscillator model.

  19. Broadband cavity-enhanced absorption spectroscopy in the ultraviolet spectral region for measurements of nitrogen dioxide and formaldehyde

    Science.gov (United States)

    Washenfelder, R. A.; Attwood, A. R.; Flores, J. M.; Zarzana, K. J.; Rudich, Y.; Brown, S. S.

    2016-01-01

    Formaldehyde (CH2O) is the most abundant aldehyde in the atmosphere, and it strongly affects photochemistry through its photolysis. We describe simultaneous measurements of CH2O and nitrogen dioxide (NO2) using broadband cavity-enhanced absorption spectroscopy in the ultraviolet spectral region. The light source consists of a continuous-wave diode laser focused into a Xenon bulb to produce a plasma that emits high-intensity, broadband light. The plasma discharge is optically filtered and coupled into a 1 m optical cavity. The reflectivity of the cavity mirrors is 0.99930 ± 0.00003 (1- reflectivity = 700 ppm loss) at 338 nm, as determined from the known Rayleigh scattering of He and zero air. This mirror reflectivity corresponds to an effective path length of 1.43 km within the 1 m cell. We measure the cavity output over the 315-350 nm spectral region using a grating monochromator and charge-coupled device array detector. We use published reference spectra with spectral fitting software to simultaneously retrieve CH2O and NO2 concentrations. Independent measurements of NO2 standard additions by broadband cavity-enhanced absorption spectroscopy and cavity ring-down spectroscopy agree within 2 % (slope for linear fit = 1.02 ± 0.03 with r2 = 0.998). Standard additions of CH2O measured by broadband cavity-enhanced absorption spectroscopy and calculated based on flow dilution are also well correlated, with r2 = 0.9998. During constant mixed additions of NO2 and CH2O, the 30 s measurement precisions (1σ) of the current configuration were 140 and 210 pptv, respectively. The current 1 min detection limit for extinction measurements at 315-350 nm provides sufficient sensitivity for measurement of trace gases in laboratory experiments and ground-based field experiments. Additionally, the instrument provides highly accurate, spectroscopically based trace gas detection that may complement higher precision techniques based on non-absolute detection methods. In addition to

  20. Using Pyridinium Styryl Dyes as the Standards of Time-Resolved Instrument Response.

    Science.gov (United States)

    Li, Lei; Chang, Mengfang; Yi, Hua; Jia, Menghui; Cao, Xiaodan; Zhou, Zhongneng; Zhang, Sanjun; Pan, Haifeng; Shih, Chun-Wei; Jimenez, Ralph; Xu, Jianhua

    2016-07-01

    In this paper, two pyridinium styryl dyes, [2-(4-dimethylamino-phenyl)-vinyl]-1-methylpyridinium iodide (DASPMI), were synthesized and characterized by steady state fluorescence spectroscopy as well as picosecond and femtosecond time-resolved fluorescence spectroscopies. Both dyes exhibit large Stokes shifts and fluorescence decays equivalent to the instrument response function (IRF) standards employed in time-correlated single-photon counting. Due to their styryl and pyridinium moieties, DASPMIs have higher peak fluorescence intensity and shorter excited-state lifetimes than iodide ion-quenched fluorophores. The fluorescence lifetimes of o-DASPMI and p-DASPMI were measured to be 6.6 ps and 12.4 ps, respectively. The fluorescence transients of these DASPMIs were used as the IRFs for iterative reconvolution fitting of the time-resolved fluorescence decay profiles of Rhodamine B (RhB), sulforhodamine B (SRB), and the SRB-SRB2m RNA aptamer complex. The quality of the fits employing the DASPMI-derived IRFs are consistently equivalent to those employing IRFs obtained from light scattering. These results indicate that DASPMI-derived IRFs may be suited for a broad range of applications in time-resolved spectroscopy and fluorescence lifetime imaging microscopy (FLIM), especially in the visible emission range. PMID:27231333

  1. Phase angle description of perturbation correlation analysis and its application to time-resolved infrared spectra.

    Science.gov (United States)

    Morita, Shigeaki; Tanaka, Masaru; Noda, Isao; Ozaki, Yukihiro

    2007-08-01

    A method of spectral analysis, phase angle description of perturbation correlation analysis, is proposed. This method is based on global phase angle description of generalized two-dimensional (2D) correlation spectroscopy, proposed by Shin-ichi Morita et al., and perturbation-correlation moving-window 2D (PCMW2D) correlation spectroscopy, proposed by Shigeaki Morita et al. For a spectral data set collected under an external perturbation, such as time-resolved infrared spectra, this method provides only one phase angle spectrum. A phase angle of the Fourier frequency domain correlation between a spectral intensity (e.g., absorbance) variation and a perturbation variation (e.g., scores of the first principle component) as a function of spectral variable (e.g., wavenumber) is plotted. Therefore, a degree of time lag of each band variation with respect to the perturbation variation is directly visualized in the phase angle spectrum. This method is applied to time-resolved infrared spectra in the O-H stretching region of the water sorption process into a poly(2-methoxyethyl acrylate) (PMEA) film. The time-resolved infrared (IR) spectra show three broad and overlapping bands in the region. Each band increases toward saturated water sorption with different relaxation times. In comparison to conventional methods of generalized 2D correlation spectroscopy and global phase angle mapping, the method proposed in the present study enables the easier visualization of the sequence as a degree of phase angle in the spectrum. PMID:17716406

  2. EPICS oscilloscope for time-resolved data acquisition

    International Nuclear Information System (INIS)

    The Sector 7 undulator beamline (7 ID) of the Advanced Photon Source (APS) is dedicated to time-resolved X-ray research . Silicon avalanche photodiodes (APDs) are used as the primary point detector for time-resolved Bragg diffraction experiments for their fast recovery time (5 photons/s) at the detector, however, deadtime corrections to the counting statistics become appreciable . Common practice has been to attenuate the monochromatic beam entering the experimental hutch to an appropriately low flux . For these high-flux experiments, an APD operated in proportional mode is a better detector choice due to a large dynamic range and linearity. With the ZT4212 ZTEC, EPICS based oscilloscope, the operating procedure to use an APD in proportional mode has been improved. This article shows the setup and operating procedure for this oscilloscope and demonstrates its application to measuring time-resolved rocking curves of laser excited semiconductors.

  3. Time-resolved electron transport in quantum-dot systems

    International Nuclear Information System (INIS)

    In this thesis the time-resolved electron transport in quantum dot systems was studied. For this two different formalisms were presented: The nonequilibrium Green functions and the generalized quantum master equations. For both formalisms a propagation method for the numerical calculation of time-resolved expectation values, like the occupation and the electron current, was developed. For the demonstration of the propagation method two different question formulations were considered. On the one hand the stochastically driven resonant-level model was studied. On the other hand the pulse-induced transport through a double quantum dot was considered.

  4. Ultra-broadband THz time-domain spectroscopy of common polymers using THz air photonics

    DEFF Research Database (Denmark)

    D’Angelo, Francesco; Mics, Zoltán; Bonn, Mischa;

    2014-01-01

    Terahertz-range dielectric properties of the common polymers low-density polyethylene (LDPE), cyclic olefin/ethylene copolymer (TOPAS®), polyamide-6 (PA6), and polytetrafluoroethylene (PTFE or Teflon®) are characterized in the ultra-broadband frequency window 2-15 THz, using a THz time...

  5. Theory of time-resolved inelastic x-ray diffraction

    DEFF Research Database (Denmark)

    Lorenz, Ulf; Møller, Klaus Braagaard; Henriksen, Niels Engholm

    2010-01-01

    Starting from a general theory of time-resolved x-ray scattering, we derive a convenient expression for the diffraction signal based on a careful analysis of the relevant inelastic scattering processes. We demonstrate that the resulting inelastic limit applies to a wider variety of experimental c...

  6. On the interpretation of time-resolved anisotropic diffraction patterns

    DEFF Research Database (Denmark)

    Lorenz, Ulf; Møller, Klaus Braagaard; Henriksen, Niels Engholm

    2010-01-01

    In this paper, we review existing systematic treatments for the interpretation of anisotropic diffraction patterns from partially aligned symmetric top molecules. Such patterns arise in the context of time-resolved diffraction experiments. We calculate diffraction patterns for ground-state Na...

  7. Schemes for time-resolved experiments at the TTF FEL

    Energy Technology Data Exchange (ETDEWEB)

    Brefeld, W.; Faatz, B.; Feldhaus, J.; Koerfer, M.; Moeller, T.; Pflueger, J.; Saldin, E.L.; Schneidmiller, E.A.; Schreiber, S. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Krzywinski, J. [Polska Akademia Nauk, Warsaw (Poland). Inst. Fizyki; Yurkov, M.V. [Joint Institute for Nuclear Research, Dubna (Russian Federation)

    2002-03-01

    The paper describes schemes of two-color time-resolved experiments that could be performed at the soft X-ray self-amplified spontaneous emission free electron laser (SASE FEL) at the TESLA test facility (TTF) at DESY and determines what additional FEL hardware and instrumentation developments will be required to bring these experiments to fruition. (orig.)

  8. An x-ray detector for time-resolved studies

    International Nuclear Information System (INIS)

    The development of ultrahigh-brightness x-ray sources makes time-resolved x-ray studies more and more feasible. Improvements in x-ray optics components are also critical for obtaining the appropriate beam for a particular type of experiment. Moreover, fast parallel detectors will be essential in order to exploit the combination of high intensity x-ray sources and novel optics for time-resolved experiments. A CCD detector with a time resolution of microseconds has been developed at the Advanced Photon Source (APS). This detector is fully programmable using CAMAC electronics and a Micro Vax computer. The techniques of time-resolved x-ray studies, which include scattering, microradiography, microtomography, stroboscopy, etc., can be applied to a range of phenomena (including rapid thermal annealing, surface ordering, crystallization, and the kinetics of phase transition) in order to understand these time-dependent microscopic processes. Some of these applications will be illustrated by recent results performed at synchrotrons. New powerful x-ray sources now under construction offer the opportunity to apply innovative approaches in time-resolved work

  9. Time-resolved luminescence from feldspars: New insight into fading

    DEFF Research Database (Denmark)

    Tsukamoto, S.; Denby, P.M.; Murray, A.S.;

    2006-01-01

    Time-resolved infrared optically stimulated luminescence (IR-OSL) signals of K- and Na-feldspar samples extracted from sediments were measured in UV, blue and red detection windows, using a fast photon counter and pulsed IR stimulation (lambda = 875 nm). We observe that the relative contribution...

  10. Time-Resolved 2PPE and Time-Resolved PEEM as a Probe of LSP's in Silver Nanoparticles

    Directory of Open Access Journals (Sweden)

    D. Bayer

    2008-01-01

    Full Text Available The time-resolved two-photon photoemission technique (TR-2PPE has been applied to study static and dynamic properties of localized surface plasmons (LSP in silver nanoparticles. Laterally, integrated measurements show the difference between LSP excitation and nonresonant single electron-hole pair creation. Studies below the optical diffraction limit were performed with the detection method of time-resolved photoemission electron microscopy (TR-PEEM. This microscopy technique with a resolution down to 40 nm enables a systematic study of retardation effects across single nanoparticles. In addition, as will be shown in this paper, it is a highly sensitive sensor for coupling effects between nanoparticles.

  11. Isotope identification capabilities using time resolved prompt gamma emission from epithermal neutrons

    International Nuclear Information System (INIS)

    We present a concept of integrated measurements for isotope identification which takes advantage of the time structure of spallation neutron sources for time resolved γ spectroscopy. Time resolved Prompt Gamma Activation Analysis (T-PGAA) consists in the measurement of gamma energy spectrum induced by the radioactive capture as a function of incident neutron Time Of Flight (TOF), directly related with the energy of incident neutrons. The potential of the proposed concept was explored on INES (Italian Neutron Experimental Station) at the ISIS spallation neutron source (U.K.). Through this new technique we show an increase in the sensitivity to specific elements of archaeometric relevance, through incident neutron energy selection in prompt γ spectra for multicomponent samples. Results on a standard bronze sample are presented

  12. Numerical simulations of time-resolved quantum electronics

    International Nuclear Information System (INIS)

    Numerical simulation has become a major tool in quantum electronics both for fundamental and applied purposes. While for a long time those simulations focused on stationary properties (e.g. DC currents), the recent experimental trend toward GHz frequencies and beyond has triggered a new interest for handling time-dependent perturbations. As the experimental frequencies get higher, it becomes possible to conceive experiments which are both time-resolved and fast enough to probe the internal quantum dynamics of the system. This paper discusses the technical aspects–mathematical and numerical–associated with the numerical simulations of such a setup in the time domain (i.e. beyond the single-frequency AC limit). After a short review of the state of the art, we develop a theoretical framework for the calculation of time-resolved observables in a general multiterminal system subject to an arbitrary time-dependent perturbation (oscillating electrostatic gates, voltage pulses, time-varying magnetic fields, etc.) The approach is mathematically equivalent to (i) the time-dependent scattering formalism, (ii) the time-resolved non-equilibrium Green’s function (NEGF) formalism and (iii) the partition-free approach. The central object of our theory is a wave function that obeys a simple Schrödinger equation with an additional source term that accounts for the electrons injected from the electrodes. The time-resolved observables (current, density, etc.) and the (inelastic) scattering matrix are simply expressed in terms of this wave function. We use our approach to develop a numerical technique for simulating time-resolved quantum transport. We find that the use of this wave function is advantageous for numerical simulations resulting in a speed up of many orders of magnitude with respect to the direct integration of NEGF equations. Our technique allows one to simulate realistic situations beyond simple models, a subject that was until now beyond the simulation

  13. Broadband X-ray Spectroscopy of the ADC Source 4U 1822-37 with Suzaku

    Science.gov (United States)

    Cottam, J.; White, N.

    2006-01-01

    We will present the broadband spectra of the low mass x-ray binary 4U 1822-37, recently observed with Suzaku. 4U 1822-37 is the canonical accretion disk corona (ADC) source where the compact object is obscured by an extended corona that intercepts and scatters the central continuum emission, some of which is then reprocessed in the outer regions of the accretion disk. 4U 1822-37 therefore serves as an important link between x-ray binaries and AGN. The broadband x-ray spectra from the Suzaku XIS and HXD provide a unique opportunity to probe the physical conditions in the corona and the accretion disk for this important accretion geometry.

  14. Time resolved dosimetry of human brain exposed to low frequency pulsed magnetic fields

    Science.gov (United States)

    Paffi, Alessandra; Camera, Francesca; Lucano, Elena; Apollonio, Francesca; Liberti, Micaela

    2016-06-01

    An accurate dosimetry is a key issue to understanding brain stimulation and related interaction mechanisms with neuronal tissues at the basis of the increasing amount of literature revealing the effects on human brain induced by low-level, low frequency pulsed magnetic fields (PMFs). Most literature on brain dosimetry estimates the maximum E field value reached inside the tissue without considering its time pattern or tissue dispersivity. Nevertheless a time-resolved dosimetry, accounting for dispersive tissues behavior, becomes necessary considering that the threshold for an effect onset may vary depending on the pulse waveform and that tissues may filter the applied stimulatory fields altering the predicted stimulatory waveform’s size and shape. In this paper a time-resolved dosimetry has been applied on a realistic brain model exposed to the signal presented in Capone et al (2009 J. Neural Transm. 116 257–65), accounting for the broadband dispersivity of brain tissues up to several kHz, to accurately reconstruct electric field and current density waveforms inside different brain tissues. The results obtained by exposing the Duke’s brain model to this PMF signal show that the E peak in the brain is considerably underestimated if a simple monochromatic dosimetry is carried out at the pulse repetition frequency of 75 Hz.

  15. Time resolved dosimetry of human brain exposed to low frequency pulsed magnetic fields.

    Science.gov (United States)

    Paffi, Alessandra; Camera, Francesca; Lucano, Elena; Apollonio, Francesca; Liberti, Micaela

    2016-06-21

    An accurate dosimetry is a key issue to understanding brain stimulation and related interaction mechanisms with neuronal tissues at the basis of the increasing amount of literature revealing the effects on human brain induced by low-level, low frequency pulsed magnetic fields (PMFs). Most literature on brain dosimetry estimates the maximum E field value reached inside the tissue without considering its time pattern or tissue dispersivity. Nevertheless a time-resolved dosimetry, accounting for dispersive tissues behavior, becomes necessary considering that the threshold for an effect onset may vary depending on the pulse waveform and that tissues may filter the applied stimulatory fields altering the predicted stimulatory waveform's size and shape. In this paper a time-resolved dosimetry has been applied on a realistic brain model exposed to the signal presented in Capone et al (2009 J. Neural Transm. 116 257-65), accounting for the broadband dispersivity of brain tissues up to several kHz, to accurately reconstruct electric field and current density waveforms inside different brain tissues. The results obtained by exposing the Duke's brain model to this PMF signal show that the E peak in the brain is considerably underestimated if a simple monochromatic dosimetry is carried out at the pulse repetition frequency of 75 Hz. PMID:27223143

  16. Time-Resolved Rayleigh Scattering Measurements in Hot Gas Flows

    Science.gov (United States)

    Mielke, Amy F.; Elam, Kristie A.; Sung, Chih-Jen

    2008-01-01

    A molecular Rayleigh scattering technique is developed to measure time-resolved gas velocity, temperature, and density in unseeded gas flows at sampling rates up to 32 kHz. A high power continuous-wave laser beam is focused at a point in an air flow field and Rayleigh scattered light is collected and fiber-optically transmitted to the spectral analysis and detection equipment. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. Photomultipler tubes operated in the photon counting mode allow high frequency sampling of the circular interference pattern to provide time-resolved flow property measurements. Mean and rms velocity and temperature fluctuation measurements in both an electrically-heated jet facility with a 10-mm diameter nozzle and also in a hydrogen-combustor heated jet facility with a 50.8-mm diameter nozzle at NASA Glenn Research Center are presented.

  17. Time resolved optical tomography of the human forearm

    Science.gov (United States)

    Hillman, Elizabeth M. C.; Hebden, Jeremy C.; Schweiger, Martin; Dehghani, Hamid; Schmidt, Florian E. W.; Delpy, David T.; Arridge, Simon R.

    2001-04-01

    A 32-channel time-resolved optical imaging instrument has been developed principally to study functional parameters of the new-born infant brain. As a prelude to studies on infants, the device and image reconstruction methodology have been evaluated on the adult human forearm. Cross-sectional images were generated using time-resolved measurements of transmitted light at two wavelengths. All data were acquired using a fully automated computer-controlled protocol. Images representing the internal scattering and absorbing properties of the arm are presented, as well as images that reveal physiological changes during a simple finger flexion exercise. The results presented in this paper represent the first simultaneous tomographic reconstruction of the internal scattering and absorbing properties of a clinical subject using purely temporal data, with additional co-registered difference images showing repeatable absorption changes at two wavelengths in response to exercise.

  18. Electronic State-Resolved Electron-Phonon Coupling in an Organic Charge Transfer Material from Broadband Quantum Beat Spectroscopy.

    Science.gov (United States)

    Rury, Aaron S; Sorenson, Shayne; Driscoll, Eric; Dawlaty, Jahan M

    2015-09-17

    The coupling of electron and lattice phonon motion plays a fundamental role in the properties of functional organic charge-transfer materials. In this Letter we extend the use of ultrafast vibrational quantum beat spectroscopy to directly elucidate electron-phonon coupling in an organic charge-transfer material. As a case study, we compare the oscillatory components of the transient reflection (TR) of a broadband probe pulse from single crystals of quinhydrone, a 1:1 cocrystal of hydroquinone and p-benzoquinone, after exciting nonresonant impulsive stimulated Raman scattering and resonant electronic transitions using ultrafast pulses. Spontaneous resonance Raman spectra confirm the assignment of these oscillations as coherent lattice phonon excitations. Fourier transforms of the vibrational quantum beats in our broadband TR measurements allow construction of spectra that we show report the ability of these phonons to directly modulate the electronic structure of quinhydrone. These results demonstrate how coherent ultrafast processes can characterize the complex interplay of charge transfer and lattice motion in materials of fundamental relevance to chemistry, materials sciences, and condensed matter physics. PMID:26722724

  19. Theory of time-resolved inelastic x-ray diffraction

    OpenAIRE

    Lorenz, Ulf; Møller, Klaus Braagaard; Henriksen, Niels Engholm

    2010-01-01

    Starting from a general theory of time-resolved x-ray scattering, we derive a convenient expression for the diffraction signal based on a careful analysis of the relevant inelastic scattering processes. We demonstrate that the resulting inelastic limit applies to a wider variety of experimental conditions than similar, previously derived formulas, and it directly allows the application of selection rules when interpreting diffraction signals. Furthermore, we present a simple extension to syst...

  20. Stationary and time-resolved fluorescence for humic substances characterization

    OpenAIRE

    Kumke, Michael U.; Frimmel, Fritz Hartmann

    2007-01-01

    Steady-state and time-resolved fluorescence methods were applied to investigate the fluorescence properties of humic substances of different origins. Using standard 2D emission and total luminescence spectra, fluorescence maxima, the width of the fluorescence band and a relative fluorescence quantum efficiency were determined. Different trends for fulvic acids and humic acids were observed indicating differences in the heterogeneity of the sample fractions. The complexity of the fluorescence ...

  1. Time-resolved diffraction experiments on piezoelectric actuators

    OpenAIRE

    Rödl, Florian

    2010-01-01

    One of the most important features of many common functional ceramics is piezoelectricity, a phenomenon which is not fully under-stood so far. Especially the time-dependent response and its role in the deterioration of properties due to fatigue has not been much investigated. The present work focuses especially on time-resolved X-ray-diffraction, but also uses static methods to improve the understanding of dynamic processes that occur during switching in piezoelectric actuators and how they c...

  2. Time resolved heat exchange in driven quantum systems

    International Nuclear Information System (INIS)

    We study time-dependent heat transport in systems composed of a resonant level periodically forced with an external power source and coupled to a fermionic continuum. This simple model contains the basic ingredients to understand time resolved energy exchange in quantum capacitors that behave as single particle emitters. We analyse the behaviour of the dynamic heat current for driving frequencies within the non-adiabatic regime, showing that it does not obey a Joule dissipation law

  3. Broadband continuously frequency tunable gyrotron for 600 MHz DNP-NMR spectroscopy

    International Nuclear Information System (INIS)

    A broadband continuously frequency tunable gyrotron with a triode-type magnetron injection gun was developed as power source for analysis of protein structures. The TE7,3 oscillation mode was selected to avoid mode competitions in the high magnetic field side. Axial modes of the TE7,3,-10 were sequentially excited by changing the cavity magnetic field, and frequency tuning of about 4 GHz around 395 GHz was observed with output power greater than 50 W. The frequency also varied about 1 GHz as the anode-cathode voltage varied. Thus, the broadest tuning bandwidth in the 400 GHz band gyrotrons was achieved. (author)

  4. Time-resolved MR angiography with limited projections.

    Science.gov (United States)

    Huang, Yuexi; Wright, Graham A

    2007-08-01

    A method for reconstruction of time-resolved MRI called highly-constrained backprojection (HYPR) has been developed. To evaluate the HYPR reconstruction in relation to data sparsity and temporal dynamics, computer simulations were performed, investigating signal modulations under different situations that reflect dynamic contrast-enhanced MR angiography (MRA). In vivo studies were also performed with gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA) for abdominal MRA in a canine model to demonstrate the application of HYPR for three-dimensional (3D) time-resolved MRA. When contrast dynamics vary over space, large vessels (e.g., veins) tend to introduce signal interference to small vessels (e.g., arteries) in HYPR, particularly when the vessels are in close proximity. The enhancement of background tissue signals may also alter the arterial and venous temporal profiles in HYPR. However, the artifacts are manifest as intensity modulation rather than structural interference, and therefore have little impact on structural diagnosis. Increasing the number of projections per time point increases temporal blur while reducing corruption of temporal behavior from adjacent tissues. Uniformly interleaved acquisition order, such as the bit-reversed order, is important to reduce artifacts. With high signal-to-noise ratio (SNR) and limited artifacts, HYPR reconstruction has potential to greatly improve time-resolved MRA in clinical practice. PMID:17654575

  5. Time-resolved luminescence of Cr3+ in topaz Al2SiO4(OH,F)2

    International Nuclear Information System (INIS)

    Laser-induced time-resolved luminescence, decay times and optical spectroscopy of natural topaz Al2SiO4(OH,F)2 show the presence of several luminescence centers: single Cr3+ in intermediate crystal field position, Cr-Cr pairs and radiation induced center. The possible connection of the last center with Mn4+ and V2+ is discussed

  6. Broadband pump-probe spectroscopy with sub-10-fs resolution for probing ultrafast internal conversion and coherent phonons in carotenoids

    International Nuclear Information System (INIS)

    We use pump-probe spectroscopy with broadband detection to study electronic energy relaxation and coherent vibrational dynamics in carotenoids. A fast optical multichannel analyzer combined with a non-collinear optical parametric amplifier allows simultaneous acquisition of the differential transmission dynamics on the 500-700 nm wavelength range with sub-10-fs temporal resolution. The broad spectral coverage enables on the one hand a detailed study of the ultrafast bright-to-dark state internal conversion process; on the other hand, the tracking of the motion of the vibrational wavepacket launched on the ground state multidimensional potential energy surface. We present results on all-trans β-carotene and on a long-chain polyene in solution. The developed experimental setup enables the straightforward acquisition and analysis of coherent vibrational dynamics, highlighting time-frequency domain features with extreme resolution

  7. Timely resolved measurements on CdSe nanoparticles

    International Nuclear Information System (INIS)

    By means of infrared spectroscopy the influence of the organic cover on structure and dynamics of CdSe nanoparticles was studied. First a procedure was developed, which allows to get from the static infrared spectrum informations on the quality of the organic cover and the binding behaviour of the ligands. On qualitatively high-grade and well characterized samples thereafter the dynamics of the lowest-energy electron level 1Se was time-resolvedly meausred in thew visible range. As reference served CdSe TOPO, which was supplemented by samples with the ligands octanthiole, octanic acid, octylamine, naphthoquinone, benzoquinone, and pyridine. The studied nanoparticles had a diameter of 4.86 nm. By means of the excitation-scanning or pump=probe procedure first measurements in the picosecond range were performed. The excitation wavelengths were thereby spectrally confined and so chosen that selectively the transitions 1S3/2-1S-e and 1P3/2-1Pe but not the intermediately lyingt transition 2S3/2-1Se were excited. The excitation energies were kept so low that the excitation of several excitons in one crystal could be avoided. The scanning wavelength in the infrared corresponded to the energy difference between the electron levels 1Se and 1Pe. The transients in the picosecond range are marked by a steep increasement of the signal, on which a multi-exponential decay follows. The increasement, which reproduces the popiulation of the excited state, isa inependent on the choice of the ligands. The influence of the organic cover is first visible in the different decay times of the excited electron levels. the decay of the measurement signal of CdSe TOPO can be approximatively described by three time constants: a decay constant in the early picosecond region, a time constant around hundert picoseconds, and a time constant of some nanoseconds. At increasing scanning wavelength the decay constants become longer. By directed excitation of the 1S3/2-1Se and the 1P3/2-1Pe transition

  8. Characterization of a swept external cavity quantum cascade laser for rapid broadband spectroscopy and sensing.

    Science.gov (United States)

    Brumfield, Brian E; Taubman, Matthew S; Suter, Jonathan D; Phillips, Mark C

    2015-10-01

    The performance of a rapidly swept external cavity quantum cascade laser (ECQCL) system combined with an open-path Herriott cell was evaluated for time-resolved measurements of chemical species with broad and narrow absorption spectra. A spectral window spanning 1278 - 1390 cm(-1) was acquired at a 200 Hz acquisition rate, corresponding to a tuning rate of 2x10(4) cm(-1)/s, with a spectral resolution of 0.2 cm(-1). The capability of the ECQCL to measure < 100 ppbv changes in nitrous oxide (N(2)O) and 1,1,1,2-tetrafluoroethane (F134A) concentrations on millisecond timescales was demonstrated in simulated plume studies with releases near the open-path Herriott cell. Absorbance spectra measured using the ECQCL system exhibited noise-equivalent absorption coefficients of 5x10(-9) cm(-1)Hz(-1/2). For a spectrum acquisition time of 5 ms, noise-equivalent concentrations (NEC) for N(2)O and F134A were measured to be 70 and 16 ppbv respectively, which improved to sub-ppbv levels with averaging to 100 s. Noise equivalent column densities of 0.64 and 0.25 ppmv × m in 1 sec are estimated for N(2)O and F134A. PMID:26480072

  9. Development of a Tunable Ultra-Broadband Mid IR Pulsed Source for Nonlinear Spectroscopy

    Science.gov (United States)

    Cheng, Mark; Reynolds, Anthony; Widgren, Heather; Khalil, Munira

    2012-02-01

    We generate ultra- broadband mid-IR pulses tunable from 2.5 -- 8 μm by focusing 800 nm/400 nm pulses into various gas media. The input 800 nm light is doubled to 400 nm in a type I BBO crystal. The two orthogonally polarized φ/2φ pulses encounter a birefringent calcite crystal for time delay compensation and are subsequently focused in various gas media (air, argon, neon and nitrogen) contained within a 1.2 m gas cell using a 1 m focal length silver mirror. The tunability of the broadband mid-IR pulses arises from different gases, pressure of gases and the amount of incident 800 nm/400 nm light focused into the gas cell at a given pressure. We measure IR energies as high as 0.5 μJ/pulse for an input 800 nm energy of 3 mJ/pulse in 900 Torr of Argon. The mid IR pulses exhibit ˜2% long term stability. The ultrabroadband IR pulses have a spectral bandwidth of ˜2000 cm-1 corresponding to a sub-cycle pulse centered at 4.5 μm. We will present our preliminary efforts on using the ultrabroadband IR pulses in nonlinear experiments. The broad spectral content of this novel source affords the possibility of probing multiple vibrations in a coherent manner.

  10. Time-resolved mass spectroscopic studies of an atmospheric-pressure helium microplasma jet

    OpenAIRE

    Oh, Jun-Seok; Aranda-Gonzalvo, Yolanda; James W. Bradley

    2011-01-01

    Abstract Using molecular beam mass spectroscopy, time-resolved measurements of the ionic species 12 in the plasma plume of an atmospheric-pressure helium microplasma jet have been made for 13 a range of excitation frequencies (5, 10 and 25 kHz) and source-instruments orifice distances 14 (1, 7 and 11 mm). Ionic species can only be observed in the visible plasma plume, with the 15 main positive species being N 2 + (65.26%) and O 2 + (21.11%), and few percentages of N +, O +, 16 NO + and He ...

  11. Spectroscopic Analysis of Time-Resolved Emission from Shocked Explosive Samples

    Science.gov (United States)

    Kay, Jeffrey; Jilek, Brook; Wixom, Ryan; Knepper, Robert; Tappan, Alexander; Damm, David

    2015-06-01

    We report a series of time-resolved spectroscopic measurements that aim to characterize the reactions that occur during shock initiation of high explosives. The experiments employ time- and wavelength-resolved emission spectroscopy to analyze light emitted from shocked and detonating thin explosive films. In this talk we present analysis of optical emission spectra from hexanitroazobenzene (HNAB), hexanitrostilbene (HNS), and pentaerythritol tetranitrate (PETN) samples. The emission features observed in the spectra are assigned to electronic transitions of molecular fragments, and the implications of these findings on our understanding of the underlying reaction mechanisms are discussed.

  12. Singlet Exciton Migration in a Conjugated Polymer by Picosecond Time-Resolved Photoluminescence

    Institute of Scientific and Technical Information of China (English)

    马国宏; 钱士雄; 雷洪; 汪河洲; 王荣秋; 李永舫

    2001-01-01

    The transient photoluminescence (PL) of DO-PPV (poly-(2,5-dioctyloxy-1,4-phenylene vinylene)) solution in chloroform was investigated by picosecond time-resolved PL spectroscopy. An ultrafast rise of PL and the following single exponential decay with a time constant of about 400ps were assigned to the formation of the intrachain exciton and its decay process, respectively. The redshift of the PL emission spectrum with time was caused by the subsequent exciton migration among the different conjugated segments in the DO-PPV polymer.

  13. Cervical cancer detection by time-resolved spectra of blood components

    Science.gov (United States)

    Kalaivani, Rudran; Masilamani, Vadivel; AlSalhi, Mohamad Saleh; Devanesan, Sandhanasamy; Ramamurthy, P.; Palled, Siddanna R.; Ganesh, K. M.

    2014-05-01

    Fluorescence spectral techniques are very sensitive, and hence they are gaining importance in cancer detection. The biomarkers indicative of cancer could be identified and quantified by spectral or time domain fluorescence spectroscopy. The results of an investigation of time-resolved spectra of cellular components of blood obtained from cervical cancer patients and normal controls are given. The cancer indicative biomarker in this paper is porphyrin; it has a fluorescence decay time of 60% more in samples of cancer patients than those of normal controls. Based on such measurements, a randomized set comprising samples from cancer patients and controls (N=27 in total) could be classified with sensitivity (92%) and specificity (86%).

  14. Time-resolved measurements of the ionization front in transport studies

    International Nuclear Information System (INIS)

    Characterization of the ionization front associated with thermal transport in laser-irradiated CH targets, as measured by x-ray emission from imbedded thin metallic layers, will be discussed. Observations of time-resolved filter spectrometry and time-integrated crystal spectroscopy of continuum and line emission from targets uniformly irradiated by the 24-beam 1053 nm and 6-beam 351 nm OMEGA laser will be compared, and contrasted with LTE calculations from the code LILAC; in particular, thin layer experiments suggest an observable competition between rates of ionization and hydrodynamic expansion

  15. Time-resolved luminescence studies of Eu3+ in soda-lime silicate glasses

    Science.gov (United States)

    Ruivo, Andreia; Muralha, Vânia S. F.; Águas, Hugo; de Matos, António Pires; Laia, César A. T.

    2014-02-01

    Soda-lime glasses doped with Eu3+ were synthesized using a variety of compositions, namely changing the fraction of CaO or Eu2O3. Those glasses were characterized with several techniques, including ellipsometry, UV-vis-NIR absorption spectroscopy, steady-state photoluminescence spectroscopy and time-resolved luminescence. The compositions' effects on optical properties such as refraction indexes, Eu3+ oscillator strengths and luminescence lifetimes were accessed from the analysis of the experimental results. Judd-Ofelt theory was used to analyze all these aspects, which allow the detection of a mismatch of optical properties from absorption and emission spectroscopy. This mismatch was confirmed from the time-resolved data, showing the existence of two different spectroscopic Eu3+ species. From those results it is concluded that there is evidence for lanthanide aggregation, giving rise to self-quenching effects that may be described through resonance energy transfer mechanisms. The difference between luminescence lifetimes for isolated and aggregated Eu(III) is interpreted as due to different interactions with oxygen in the matrix, namely degree of covalency of the Eu-O bond and point group symmetry of the lanthanide.

  16. Mid-infrared Fourier transform spectroscopy with a broadband frequency comb.

    Science.gov (United States)

    Adler, Florian; Masłowski, Piotr; Foltynowicz, Aleksandra; Cossel, Kevin C; Briles, Travis C; Hartl, Ingmar; Ye, Jun

    2010-10-11

    We present a first implementation of optical-frequency-comb-based rapid trace gas detection in the molecular fingerprint region in the mid-infrared. Near-real-time acquisition of broadband absorption spectra with 0.0056 cm(-1) maximum resolution is demonstrated using a frequency comb Fourier transform spectrometer which operates in the 2100-to-3700-cm(-1) spectral region. We achieve part-per-billion detection limits in 30 seconds of integration time for several important molecules including methane, ethane, isoprene, and nitrous oxide. Our system enables precise concentration measurements even in gas mixtures that exhibit continuous absorption bands, and it allows detection of molecules at levels below the noise floor via simultaneous analysis of multiple spectral features. PMID:20941086

  17. Femtosecond time-resolved MeV electron microscopy

    International Nuclear Information System (INIS)

    The direct visualization of fundamental dynamic processes in matter occurring on femtosecond time scales over sub-nanometer (even atomic) spatial dimensions has long been a goal in science. In this paper, the development of a femtosecond time-resolved relativistic transmission electron microscopy (FsTEM) based on a photocathode radio-frequency (RF) gun is reported. The requirements and limitations of the beam parameters used in FsTEM are discussed. Finally, some demonstrations of relativistic ultrafast electron diffraction measurement using the RF gun are presented. (author)

  18. TIME-RESOLVED PHOTOLUMINESCENCE OF SINTERED ZnO CERAMICS

    Institute of Scientific and Technical Information of China (English)

    WEN XIAO-MING(文小明); N.OHNO; ZHANG ZHONG-MING(张中明)

    2001-01-01

    The time-resolved photoluminescence (TRPL) of sintered ZnO ceramics was measured at low temperatures. A broad luminescence band was observed in the visible region. The TRPL experiment shows that photolurninescence decay behaviour can be depicted as t-π(r). The decay rate n(r) and lifetime are wavelength dependent, and the former varies exponentially with wavelength. The power-lowering behaviour of the luminescence intensity indicates that the luminescence band originates from the recombination of donor-acceptor pairs.

  19. Femtosecond time-resolved electronic relaxation dynamics in tetrathiafulvalene

    Energy Technology Data Exchange (ETDEWEB)

    Staedter, D.; Polizzi, L. [Laboratoire de Collisions, Agrégats et Réactivité, IRSAMC, Université de Toulouse-CNRS, 31062 Toulouse (France); Thiré, N. [Laboratoire de Collisions, Agrégats et Réactivité, IRSAMC, Université de Toulouse-CNRS, 31062 Toulouse (France); INRS-EMT, Advanced Laser Light Source, 1650 Lionel-Boulet Blvd., Varennes, Quebec J3X1S2 (Canada); Mairesse, Y. [Centre des Laser Intenses et Applications, Université de Bordeaux-CNRS, 33405 Talence (France); Mayer, P. [Chemistry Department, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada); Blanchet, V., E-mail: blanchet@celia.u-bordeaux1.fr [Laboratoire de Collisions, Agrégats et Réactivité, IRSAMC, Université de Toulouse-CNRS, 31062 Toulouse (France); Centre des Laser Intenses et Applications, Université de Bordeaux-CNRS, 33405 Talence (France)

    2015-05-21

    In the present paper, the ultrafast electronic relaxation of tetrathiafulvalene (TTF) initiated around 4 eV is studied by femtosecond time-resolved velocity-map imaging. The goal is to investigate the broad double structure observed in the absorption spectrum at this energy. By monitoring the transients of the parent cation and its fragments and by varying the pump and the probe wavelengths, two internal conversions and intramolecular vibrational relaxation are detected both on the order of a few hundred of femtoseconds. Photoelectron images permit the assignment of a dark electronic state involved in the relaxation. In addition, the formation of the dimer of TTF has been observed.

  20. Embedded remote control of time-resolved OTR measurement system

    International Nuclear Information System (INIS)

    The on-line measurement system based on OTR can be used to measure the parameters of the intense electron beam, such as beam energy, divergence and emittance, and it has characteristics of ultra-fast response and high special resolution. With the embedded remote controll system, the time-resolved OTR measurement has been implemented successfully. The computer controll system receives the photoelectric video frequency signal, transmits real time image, and gets the dynamic image. This work removes the difficulties of strong disturbance in the beam measurement of intense LIA. (authors)

  1. A compact electron gun for time-resolved electron diffraction

    International Nuclear Information System (INIS)

    A novel compact time-resolved electron diffractometer has been built with the primary goal of studying the ultrafast molecular dynamics of photoexcited gas-phase molecules. Here, we discuss the design of the electron gun, which is triggered by a Ti:Sapphire laser, before detailing a series of calibration experiments relating to the electron-beam properties. As a further test of the apparatus, initial diffraction patterns have been collected for thin, polycrystalline platinum samples, which have been shown to match theoretical patterns. The data collected demonstrate the focusing effects of the magnetic lens on the electron beam, and how this relates to the spatial resolution of the diffraction pattern

  2. Broadband Bioimpedance Spectroscopy Based on a Multifrequency Mixed Excitation and Nuttall Windowed FFT Algorithm

    OpenAIRE

    Yuxiang Yang; Wen Zhang; Fangling Du; Xuan Tang; He Wen; Zhaosheng Teng

    2014-01-01

    Bioimpedance spectroscopy (BIS) has become an important clinical indicator for monitoring the pathological status of biological tissues, and multifrequency simultaneous measurement of BIS may provide more accurate diagnostic information compared with the traditional frequency-sweep measurement technology. This paper proposes a BIS multifrequency simultaneous measurement method based on multifrequency mixed (MFM) signal excitation and a Nuttall windowed interpolation FFT algorithm. Firstly, th...

  3. Millifluidics for time-resolved mapping of the growth of gold nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sai Krishna, Katla; Navin, Chelliah; Biswas, Sanchita; Singh, Varshni; Ham, Kyungmin; Bovencamp, L. S.; Theegala, Chandra; Miller, Jeffrey T; Spivey, James J.; Kumar, Challa S.S.R.

    2013-04-10

    Innovative in situ characterization tools are essential for understanding the reaction mechanisms leading to the growth of nanoscale materials. Though techniques, such as in situ transmission X-ray microscopy, fast single-particle spectroscopy, small-angle X-ray scattering, etc., are currently being developed, these tools are complex, not easily accessible, and do not necessarily provide the temporal resolution required to follow the formation of nanomaterials in real time. Here, we demonstrate for the first time the utility of a simple millifluidic chip for an in situ real time analysis of morphology and dimension-controlled growth of gold nano- and microstructures with a time resolution of 5 ms. The structures formed were characterized using synchrotron radiation-based in situ X-ray absorption spectroscopy, 3-D X-ray tomography, and high-resolution electron microscopy. These gold nanostructures were found to be catalytically active for conversion of 4-nitrophenol into 4-aminophenol, providing an example of the potential opportunities for time-resolved analysis of catalytic reactions. While the investigations reported here are focused on gold nanostructures, the technique can be applied to analyze the time-resolved growth of other types of nanostructured metals and metal oxides. With the ability to probe at least a 10-fold higher concentrations, in comparison with traditional microfluidics, the tool has potential to revolutionize a broad range of fields from catalysis, molecular analysis, biodefense, and molecular biology.

  4. Time-resolved HAXPES at SACLA: probe and pump pulse-induced space-charge effects

    International Nuclear Information System (INIS)

    Time-resolved hard x-ray photoelectron spectroscopy (trHAXPES) is established using the x-ray free-electron laser SACLA. The technique extends time-resolved photoemission into the hard x-ray regime and, as a core-level spectroscopy, combines element and atomic-site specificity and sensitivity to the chemical environment with femtosecond time resolution and bulk (sub-surface) sensitivity. The viability of trHAXPES using 8 keV x-ray free-electron-laser radiation is demonstrated by a systematic investigation of probe and pump pulse-induced vacuum space-charge effects on the V 1s emission of VO2 and the Ti 1s emission of SrTiO3. The time and excitation energy dependencies of the measured spectral shifts and broadenings are compared to the results of N-body numerical simulations and simple analytic (mean-field) models. Good agreement between the experimental and calculated results is obtained. In particular, the characteristic temporal evolution of the pump pulse-induced spectral shift is shown to provide an effective means to determine the temporal overlap of pump and probe pulses. trHAXPES opens a new avenue in the study of ultrafast atomic-site specific electron and chemical dynamics in materials and at buried interfaces. (paper)

  5. Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility

    Energy Technology Data Exchange (ETDEWEB)

    Grills, David C., E-mail: dcgrills@bnl.gov; Farrington, Jaime A.; Layne, Bobby H.; Preses, Jack M.; Wishart, James F. [Chemistry Department, Brookhaven National Laboratory, P.O. Box 5000, Upton, New York 11973-5000 (United States); Bernstein, Herbert J. [Department of Mathematics and Computer Science, Dowling College, 1300 William Floyd Parkway, Shirley, New York 11967 (United States)

    2015-04-15

    When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult. Time-resolved vibrational spectroscopy would offer much improved structural characterization, but has received only limited application in pulse radiolysis. In this paper, we describe in detail the development of a unique nanosecond time-resolved infrared (TRIR) detection capability for condensed-phase pulse radiolysis on a new beam line at the LEAF facility of Brookhaven National Laboratory. The system makes use of a suite of high-power, continuous wave external-cavity quantum cascade lasers as the IR probe source, with coverage from 2330 to 1051 cm{sup −1}. The response time of the TRIR detection setup is ∼40 ns, with a typical sensitivity of ∼100 μOD after 4-8 signal averages using a dual-beam probe/reference normalization detection scheme. This new detection method has enabled mechanistic investigations of a range of radiation-induced chemical processes, some of which are highlighted here.

  6. Director tumbling of nematic wormlike micelles under shear: time-resolved rheo-NMR experiments

    International Nuclear Information System (INIS)

    Nematic liquid crystals show a complex flow behavior due to the coupling between orientation and flow. Some materials show a stable director orientation in steady shear flow (flow aligning), while for others no stable director orientation exists (tumbling). Director tumbling gives rise to oscillations of shear and normal stresses in rheological experiments and can be detected by optical methods, for example by microscopy or birefringence measurements. We have used deuterium NMR spectroscopy to observe shear-induced director orientations. In the lyotropic system cetylpyridinium chloride/hexanol/brine, which forms a nematic phase of wormlike micelles, time-resolved observations of the director orientation by means of deuterium NMR spectroscopy of D2O have been possible for the first time. The time-dependence of the director orientations in both shear start-up and flow-reversal experiments will be presented. (orig.)

  7. Exhaled breath profiling using broadband quantum cascade laser-based spectroscopy in healthy children and children with asthma and cystic fibrosis.

    Science.gov (United States)

    van Mastrigt, E; Reyes-Reyes, A; Brand, K; Bhattacharya, N; Urbach, H P; Stubbs, A P; de Jongste, J C; Pijnenburg, M W

    2016-01-01

    Exhaled breath analysis is a potential non-invasive tool for diagnosing and monitoring airway diseases. Gas chromatography-mass spectrometry and electrochemical sensor arrays are the main techniques to detect volatile organic compounds (VOC) in exhaled breath. We developed a broadband quantum cascade laser spectroscopy technique for VOC detection and identification. The objective of this study was to assess the repeatability of exhaled breath profiling with broadband quantum cascade laser-based spectroscopy and to explore the clinical applicability by comparing exhaled breath samples from healthy children with those from children with asthma or cystic fibrosis (CF). Healthy children and children with stable asthma or stable CF, aged 6-18 years, were included. Two to four exhaled breath samples were collected in Tedlar bags and analyzed by quantum cascade laser spectroscopy to detect VOCs with an absorption profile in the wavenumber region between 832 and 1262.55 cm(-1). We included 35 healthy children, 39 children with asthma and 15 with CF. Exhaled breath VOC profiles showed poor repeatability (Spearman's rho  =  0.36 to 0.46) and agreement of the complete profiles. However, we were able to discriminate healthy children from children with stable asthma or stable CF and identified VOCs that were responsible for this discrimination. Broadband quantum cascade laser-based spectroscopy detected differences in VOC profiles in exhaled breath samples between healthy children and children with asthma or CF. The combination of a relatively easy and fast method and the possibility of molecule identification makes broadband quantum cascade laser-based spectroscopy attractive to investigate the diagnostic and prognostic potential of volatiles in exhaled breath. PMID:27058305

  8. Time-resolved tomographic images of a relativistic electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, H.A.; Jacoby, B.A.; Nelson, M.

    1984-07-01

    We obtained a sequential series of time-resolved tomographic two-dimensional images of a 4.5-MeV, 6-kA, 30-ns electron beam. Three linear fiber-optic arrays of 30 or 60 fibers each were positioned around the beam axis at 0/sup 0/, 61/sup 0/, and 117/sup 0/. The beam interacting with nitrogen at 20 Torr emitted light that was focused onto the fiber arrays and transmitted to a streak camera where the data were recorded on film. The film was digitized, and two-dimensional images were reconstructed using the maximum-entropy tomographic technique. These images were then combined to produce an ultra-high-speed movie of the electron-beam pulse.

  9. Time-resolved neutron imaging at ANTARES cold neutron beamline

    CERN Document Server

    Tremsin, A S; Tittelmeier, K; Schillinger, B; Schulz, M; Lerche, M; Feller, W B

    2015-01-01

    In non-destructive evaluation with X-rays light elements embedded in dense, heavy (or high-Z) matrices show little contrast and their structural details can hardly be revealed. Neutron radiography, on the other hand, provides a solution for those cases, in particular for hydrogenous materials, owing to the large neutron scattering cross section of hydrogen and uncorrelated dependency of neutron cross section on the atomic number. The majority of neutron imaging experiments at the present time is conducted with static objects mainly due to the limited flux intensity of neutron beamline facilities and sometimes due to the limitations of the detectors. However, some applications require the studies of dynamic phenomena and can now be conducted at several high intensity beamlines such as the recently rebuilt ANTARES beam line at the FRM-II reactor. In this paper we demonstrate the capabilities of time resolved imaging for repetitive processes, where different phases of the process can be imaged simultaneously and...

  10. Femtosecond Time-resolved MeV Electron Diffraction

    CERN Document Server

    Zhu, Pengfei; Cao, J; Geck, J; Hidaka, Y; Kraus, R; Pjerov, S; Shen, Y; Tobey, R I; Zhu, Y; Hill, J P; Wang, X J

    2013-01-01

    We report the experimental demonstration of electron diffraction with 130 femtosecond time resolution using bench-top MeV electron beams. High-quality, single-shot electron diffraction patterns for both polycrystalline aluminium and single-crystal 1T-TaS_{2} are obtained utilizing a 5 femto-Coulomb (~3x10^{4} electrons) pulse of electrons at 2.8 MeV. The timing jitter between the pump laser and probe electron beam was found to be ~ 100 fs. The time resolution is demonstrated by observing the evolution of Bragg and superlattice peaks of 1T-TaS_{2} following an optical pump. Our experiemntal results demonstrate the feasibility of ultimately realizing 40 fs time-resolved electron diffraction.

  11. Time-resolved rotation projection MR phase contrast angiography

    International Nuclear Information System (INIS)

    In view of the advantages of time-resolved phase contrast angiography, the authors have investigated the additional advantage of incrementing projection angle during the cardiac cycle. An electrocardiographically triggered, multisection sequence was modified to produce bipolar gradient-reversal phase-contrast angiograms at 45-msec intervals. The projection angle for each angiogram was incremented by 5 degrees. Asymmetric echo acquisition was used to minimize TE. Velocity-compensated field-of-view select and readout gradients were used. Acceleration-compensated velocity encoding and velocity-compensated phase encoding gradients were investigated. A weak dephasing gradient was used in the projection direction. Images were acquired at 16 angles with four excitations per angle; acquisition time was approximately 8 minutes for each velocity component

  12. A prototype chopper for synchrotron time-resolved crystallographic measurements

    International Nuclear Information System (INIS)

    A mechanical x-ray chopper has been designed to perform microsecond time-resolved crystallographic studies at the DIAMOND synchrotron I19 beamline. It consists of two asymmetric absorbers rotating synchronously at frequencies from 0 to 50 Hz in the same direction around a rotation axis that is parallel to the x-ray beam. The duration of the x-ray pulses produced by the chopper is determined by the relative phase between the two blades, which can be adjusted. The chopper system presented in this paper offers a time resolution suitable for conducting in situ experiments that afford the crystal structure of materials while in their transient (>10 μs) photoactivated excited states.

  13. Fast time-resolved aerosol collector: proof of concept

    Directory of Open Access Journals (Sweden)

    X.-Y. Yu

    2010-10-01

    Full Text Available Atmospheric particles can be collected in the field on substrates for subsequent laboratory analysis via chemically sensitive single particle methods such as scanning electron microscopy with energy dispersive x-ray analysis. With moving substrates time resolution of seconds to minutes can be achieved. In this paper, we demonstrate how to increase the time resolution when collecting particles on a substrate to a few milliseconds to provide real-time information. Our fast time-resolved aerosol collector ("Fast-TRAC" microscopically observes the particle collection on a substrate and records an on-line video. Particle arrivals are resolved to within a single frame (4–17 ms in this setup, and the spatial locations are matched to the subsequent single particle analysis. This approach also provides in-situ information on particle size and number concentration. Applications are expected in airborne studies of cloud microstructure, pollution plumes, and surface long-term monitoring.

  14. Fast time-resolved aerosol collector: proof of concept

    Directory of Open Access Journals (Sweden)

    X.-Y. Yu

    2010-06-01

    Full Text Available Atmospheric particles can be collected in the field on substrates for subsequent laboratory analysis via chemically sensitive single particle methods such as scanning electron microscopy with energy dispersive x-ray analysis. With moving substrates time resolution of seconds to minutes can be achieved. In this paper, we demonstrate how to increase the time resolution when collecting particles on a substrate to a few milliseconds to provide real-time information. Our fast time-resolved aerosol collector ("Fast-TRAC" microscopically observes the particle collection on a substrate and records an on-line video. Particle arrivals are resolved to within a single frame (4–17 ms in this setup, and the spatial locations are matched to the subsequent single particle analysis. This approach also provides in-situ information on particle size and number concentration. Applications are expected in airborne studies of cloud microstructure, pollution plumes, and surface long-term monitoring.

  15. Spectral characteristics of time resolved magnonic spin Seebeck effect

    Energy Technology Data Exchange (ETDEWEB)

    Etesami, S. R.; Chotorlishvili, L.; Berakdar, J. [Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, 06099 Halle (Germany)

    2015-09-28

    Spin Seebeck effect (SSE) holds promise for new spintronic devices with low-energy consumption. The underlying physics, essential for a further progress, is yet to be fully clarified. This study of the time resolved longitudinal SSE in the magnetic insulator yttrium iron garnet concludes that a substantial contribution to the spin current stems from small wave-vector subthermal exchange magnons. Our finding is in line with the recent experiment by S. R. Boona and J. P. Heremans [Phys. Rev. B 90, 064421 (2014)]. Technically, the spin-current dynamics is treated based on the Landau-Lifshitz-Gilbert equation also including magnons back-action on thermal bath, while the formation of the time dependent thermal gradient is described self-consistently via the heat equation coupled to the magnetization dynamics.

  16. A Study of Electron and Phonon Dynamics by Broadband Two-Dimensional THz Time-Domain Spectroscopy

    Science.gov (United States)

    Fu, Zhengping

    Terahertz (THz) wave interacts with semiconductors in many ways, such as resonant excitation of lattice vibration, intraband transition and polaron formation. Different from the optical waves, THz wave has lower photon energy (1 THz = 4.14 meV) and is suitable for studying dynamics of low-energy excitations. Recently the studies of the interaction of THz wave and semiconductors have been extending from the linear regime to the nonlinear regime, owing to the advance of the high-intensity THz generation and detection methods. Two-dimensional (2D) spectroscopy, as a useful tool to unravel the nonlinearity of materials, has been well developed in nuclear magnetic resonance and infrared region. However, the counterpart in THz region has not been well developed and was only demonstrated at frequency around 20 THz due to the lack of intense broadband THz sources. Using laser-induced plasma as the THz source, we developed collinear broadband 2D THz time-domain spectroscopy covering from 0.5 THz to 20 THz. Broadband intense THz pulses emitted from laser-induced plasma provide access to a variety of nonlinear properties of materials. Ultrafast optical and THz pulses make it possible to resolve the transient change of the material properties with temporal resolution of tens of femtoseconds. This thesis focuses on the linear and nonlinear interaction of the THz wave with semiconductors. Since a great many physical processes, including vibrational motion of lattice and plasma oscillation, has resonant frequency in the THz range, rich physics can be studies in our experiment. The thesis starts from the linear interaction of the THz wave with semiconductors. In the narrow band gap semiconductor InSb, the plasma absorption edge, Restrahlen band and dispersion of polaritons are observed. The nonlinear response of InSb in high THz field is verified in the frequency-resolved THz Z-scan experiment. The third harmonic generations due to the anharmonicity of plasma oscillation and the

  17. Vacuum UV broad-band absorption spectroscopy: a powerful diagnostic tool for reactive plasma monitoring

    OpenAIRE

    Cunge, G; Fouchier, M; Brihoum, M; Bodart, P.; Touzeau, M.; N. Sadeghi

    2011-01-01

    Abstract Broad band UV-visible absorption spectroscopy is widely used to measure the concentration of radicals in reactive plasmas. We extended the applicability of this technique to the VUV (115 nm to 200 nm), the spectral range in which the electronic transitions from the ground state to the Rydberg or pre-dissociated states of many closed shell molecules are located. This gives access to the absolute densities of species which do not, or weakly absorb in the UV/visible range. The techni...

  18. Detailed optical and near-infrared polarimetry, spectroscopy and broadband photometry of the afterglow of GRB 091018: Polarisation evolution

    CERN Document Server

    Wiersema, K; Kruehler, T; Melandri, A; Rol, E; Starling, R L C; Tanvir, N R; van der Horst, A J; Covino, S; Fynbo, J P U; Goldoni, P; Gorosabel, J; Hjorth, J; Klose, S; Mundell, C G; O'Brien, P T; Palazzi, E; Wijers, R A M J; D'Elia, V; Evans, P A; Filgas, R; Gomboc, A; Greiner, J; Guidorzi, C; Kaper, L; Kobayashi, S; Kouveliotou, C; Levan, A J; Rossi, A; Rowlinson, A; Steele, I A; Postigo, A de Ugarte; Vergani, S D

    2012-01-01

    [Abridged] A number of phenomena have been observed in GRB afterglows that defy explanation by simple versions of the standard fireball model, leading to a variety of new models. Polarimetry can be a major independent diagnostic of afterglow physics, probing the magnetic field properties and internal structure of the GRB jets. In this paper we present the first high quality multi-night polarimetric light curve of a Swift GRB afterglow, aimed at providing a well calibrated dataset of a typical afterglow to serve as a benchmark system for modelling afterglow polarisation behaviour. In particular, our dataset of the afterglow of GRB 091018 (at redshift z=0.971) comprises optical linear polarimetry (R band, 0.13 - 2.3 days after burst); circular polarimetry (R band) and near-infrared linear polarimetry (Ks band). We add to that high quality optical and near-infrared broadband light curves and spectral energy distributions as well as afterglow spectroscopy. The linear polarisation varies between 0 and 3%, with bot...

  19. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Libing; Lu, Zhou; Velarde Ruiz Esparza, Luis A.; Fu, Li; Pu, Yunqiao; Ding, Shi-You; Ragauskas, Art J.; Wang, Hongfei; Yang, Bin

    2015-06-01

    Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.

  20. Muscle oxygenation during exercise under hypoxic conditions assessed by spatially resolved broadband NIR spectroscopy

    Science.gov (United States)

    Geraskin, Dmitri; Platen, Petra; Franke, Julia; Andre, Christiane; Bloch, Wilhelm; Kohl-Bareis, Matthias

    2005-08-01

    Near-infrared spectroscopy (NIRS) is used for the non-invasive measurement of muscle oxygenation during an incremental cycle test in healthy volunteers. A broad band spatially resolved system is used that allows the reliability of current algorithms to be inspected with the main emphasis on tissue oxygen saturation (SO2) and oxygenated and deoxygenated haemoglobin concentrations. Physiological conditions were modulated by changing oxygen supply from normal (21 % O2 in inspired air) to conditions corresponding to 2000 and 4000 m altitude above sea level (15.4 and 11.9 % O2). Under these hypoxic conditions the decrease in SO2 with increased exercise power is highly correlated with the oxygen content of the inspired air. There is a clear correlation with physiological parameters (heart rate, pulse oxymetry, blood gas, lactate, spirometric data). Skin oxygenation parameters are compared to those of muscle.